Hexahalo-1,4-dihydro-1,4-methano-napth-5,8-ylene acetates

ABSTRACT

A fire retardant system comprising a compound having within its structure the 1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dione or 1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dioxy nucleus or a compound which is capable of being converted to the 1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dione nucleus and requires no metal oxide addition to exert is function.

This a division, of application Ser. No. 329,177, filed Feb. 2, 1973,now U.S. Pat. No. 3,875,236, which is in turn a division of applicationSer. No. 80,747, filed Oct. 14, 1970, abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention pertains to the field of flame retardants for polymers.More particularly, this invention pertains to improved fire retardantsystems for plastics, elastomers, and articles therefrom, e.g., fibers,films, shape articles, and the like.

2. Description of the Prior Art

The increased use of polymeric materials, particularly in the buildingindustry, has resulted in greatly increased interest in the fireretardancy of these materials. However, at the present time mostcommercially available plastics do not possess satisfactory fireretardancy and this inadequacy represents one of the major obstacles tothe opening of new markets and uses for these materials.

Presently, the most widely used fire retardant chemicals are antimonytrioxide and organohalogen compounds, the best known being chlorendicanhydride(1,4,5,6,7,7-hexachlorobicyclo-[2.2.1]hept-5-ene-2,3-dicarboxylicanhydride); tetrabromo- or tetrachlorophthalic acid;1,4'-isopropylidenebis (2,6-dichlorophenol) [tetrachlorobisphenol A] orthe corresponding bromine-containing compound; chloran, i.e.,2,3-dicarboxyl-5,8-endomethylene-5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydronaphthaleneanhydride; chlorinated paraffins; and dechlorane(dihexachlorocyclopentadiene).

The foregoing halogen compounds have only limited utility in polymercompositions due to a number of disadvantages. For example, when suchhalogen compounds are incorporated into a polymer, various physicalproperties of the polymer are modified, e.g., change in melt viscositywhich requires higher processing temperatures, decrease in lightstability, decrease in thermal stability, increase in density, adverseeffects on heat distortion point, etc.

Some of these disadvantages have been overcome by the use ofhalogen-containing polymers as the flame retardant additive. Typical ofsuch polymers are 2-chlorobutadiene, polyvinylchloride, chlorinatedpolyethylene and chlorosulfonated polyethylene. There are also, however,serious disadvantages associated with the use of such polymers. Amongthese are: (1) large amounts of halogen-containing polymers are requiredin order to obtain satisfactory fire retardancy due to the relativelylow halogen content thereof; (2) the halogen-containing polymers havelow thermal stabilities; and (3) the blending of the halogen-containingpolymer with the polymer to be rendered flame retardant usually requiresexpensive processing techniques.

SUMMARY OF THE INVENTION

We have discovered a new system of chemical fire retardants forpolymeric materials, which system comprises a chemical compound havingthe 1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dione or1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dioxynucleus or a compound which is capable of being converted to the1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dionenucleus and requires no metal oxide addition to exert its function.Preferably, the compound having the foregoing nucleus or beingconvertible thereto has a molecular weight not in excess of about 2000.

The polymeric materials are rendered fire retardant by incorporation ofthe fire retardant system of the present invention into the polymer.

The fire retardant system of the present invention may readily beincorporated into the polymeric material by a variety of methodsdepending on the nature of the polymeric material. Thus, for example,for those polymers which are adaptable to milling procedures and thelike, the fire retardant system may simply be physically blended withthe preformed polymer. With other types of polymers which requirecompounding, e.g., an uncured elastomer, or cannot readily be physicallyblended with other materials after formation of the polymer, the fireretardant system may be added to the compounding mixture orpolymerization mixture.

More particularly, we have found that a polymer may be made effectivelyflame retardant by blending into the polymer either (1) a fire retardantcompound having a nucleus that is of the formula ##STR1## wherein X ishalogen, (2) a precursor of said fire retardant compound, whichprecursor, upon combustion of said blend, converts to a compoundcontaining nucleus I or II, or (3) a fire retardant compound having anucleus that is of the formula ##STR2## wherein X is halogen.

Preferred precursors contain a nucleus selected from the groupconsisting of ##STR3## wherein X is halogen.

Most preferred fire retardant compounds are those selected from thegroup consisting of ##STR4## wherein X is halogen, wherein R₁ and R₂ canbe the same or different and each may be

hydrogen,

lower alkyl,

halogen substituted lower alkyl,

halogen,

nitrile,

an aromatic nucleus of the phenyl series,

--SO₂ R₅ wherein R₅ is lower alkyl, an aromatic nucleus of the phenylseries, or halogen substituted lower alkyl, ##STR5## wherein R₆ ishydrogen, hydroxy, alkoxy, or lower alkyl, or halogen substituted loweralkyl, and wherein R₁ and R₂ taken together is ##STR6## and wherein R₃and R₄ are the same or different and each may be

hydrogen,

lower alkyl,

halogen substituted lower alkyl,

lower alkanol,

--(CH₂)_(n) COOH wherein n is an integer from 1 to 5,

--CH₂ CH=CH--R₇ wherein R₇ is hydrogen, lower alkyl, or halogensubstituted lower alkyl,

--SO₂ --R₈ wherein R₈ is lower alkyl, an aromatic nucleus of the phenylseries, or halogen substituted lower alkyl, ##STR7## wherein R₉ and R₁₀are each lower alkyl, or halogen substituted lower alkyl, ##STR8##wherein R₁₁ and R₁₂ are each lower alkoxy, ##STR9## or ##STR10## whereinR₁₃ is lower alkyl, halogen substituted lower alkyl, lower alkoxy, anaromatic nucleus of the phenyl series, or --NHR₁₄ wherein R₁₄ is loweralkyl.

We have further discovered that when our fire retardant system isincorporated in a polymeric composition containing any of the variouspreviously known fire retardant materials, described hereinabove, thefire retardancy is markedly enhanced to an unexpected degree.

The fire retardant system of the present invention may be used with awide spectrum of polymeric compositions such as, for example,hydrocarbon chain polymers, natural and synthetic rubbers, resinous orrubbery interpolymers, acrylonitrilebutadiene-styrene polymers,styrene-acrylonitrile resins, foamed and unfoamed polyurethanes,polysulfones, polysulfides, epoxy resins, polyether polyepoxides,thermoplastic and thermosetting polyesters, polycarbonates, celluloseesters, urea-formaldehyde and phenol-formaldehyde resins, polyamides,etc., as well as mixtures of the foregoing with one another.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention resides in the discovery that polymeric materialsmay be rendered flame retardant by incorporating therein a fireretardant chemical structural system comprising a compound having withinits structure the1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dione or1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dioxynucleus or a compound which is capable of being converted to the1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dionenucleus and requires no metal oxide addition to exert its function.

Certain of the materials which may be employed as our fire retardantsystem are novel compounds per se. Such novel compounds include thosecompounds defined by the following five structural formulas (formulasV-IX respectively). In these formulas "X" always designates halogen:##STR11## wherein R₁₅ and R₁₆ are hydrogen or taken together from thegroup ##STR12## Z is oxygen when R₁₅ and R₁₆ form the group IVA, and Zis =NOH when R₁₅ and R₁₆ are hydrogen; ##STR13## wherein Y is oxygen or=NOH; when Y is oxygen, then R₁₇ and R₁₃ may be hydrogen, tertiary butylwith at least one of R₁₇ and R₁₃ being tertiary butyl, or R₁₇ and R₁₈taken together form the group IVA; when Y is =NOH, then R₁₇ and R₁₈ arehydrogen; ##STR14## wherein R₁₉ and R₂₀ are the same or different andeach may be

hydrogen,

lower alkyl,

halogen substituted lower alkyl,

lower alkanol,

--(CH₂)_(n) COOH wherein n is an integer from 1 to 5,

--CH₂ CH=CH--R₂₃ wherein R₂₃ is a hydrogen, halogen substituted loweralkyl,

--SO₂ --R₂₄ wherein R₂₄ is lower alkyl, halogen substituted lower alkylor an aromatic nucleus of the phenyl series, ##STR15## wherein R₂₅ andR₂₆ are each lower alkyl, or halogen substituted lower alkyl, ##STR16##wherein R₂₇ and R₂₈ are each lower alkoxy, ##STR17## or ##STR18##wherein

R₂₉ is lower alkyl, halogen substituted lower alkyl, lower alkoxy, anaromatic nucleus of the phenyl series, or --NHR₃₀ wherein R₃₀ is loweralkyl,

R₂₁ and R₂₂ can be the same or different and each may be hydrogen, loweralkyl, halogen substituted lower alkyl, --SO₂ --R₂₄ wherein R₂₄ is asdefined hereinabove, ##STR19## wherein R₂₉ is as defined hereinabove,with the proviso that when both R₁₉ and R₂₀ are ##STR20## then R₂₁ andR₂₂ may also be halogen, and further provided that when R₁₉ and R₂₀ areboth hydrogen than at least one of R₂₁ and R₂₂ is a group other thanhydrogen or lower alkyl having 1 to 4 carbon atoms, or R₂₁ and R₂₂ takentogether form the group IVA; ##STR21## wherein R₃₁ and R₃₂ may be thesame or different and may be hydrogen lower alkyl, halogen substitutedlower alkyl, --SO₂ --R₂₄ wherein R₂₄ is as defined hereinabove, --S--R₃₃wherein R₃₃ is hydrogen, lower alkyl, or halogen substituted loweralkyl, R₃₁ and R₃₂ taken together may be --O--, ##STR22## wherein R₁₉R₂₀ R₃₁ and R₃₂ and X are defined hereinabove.

Generally, the compounds of the present invention may be prepared bymethods well known in the art for forming [2.2.1] bicyclic ringstructures, such as, for example the Diels-Alder reaction. Suchsynthesis would normally involve the reaction of ahexahalocyclopentadiene with the appropriately substituted benzoquinonecompound, to form the structure: ##STR23## wherein R_(y) and R_(z) maybe various saturated or unsaturated aliphatic compounds, an aromaticnucleus or functional groups and X is halogen. This compound may then besubjected to various reactions well known in the art for changing thedegree of saturation or functional group.

Suitable polymers in which the fire retardant systems of the presentinvention can be used include:

1. Hydrocarbon chain polymers, such as, for example, polyethylene;cross-linked polyethylene; polypropylene; ethylenepropylene copolymers;polymers of monoethyleneically unsaturated monomers such as styrene,alpha methylstyrene, acrylonitrile, isobutylene, vinyl pyridine, acrylicacid, acrylates, vinyl acetate; vinyl alcohol; vinylethers andcopolymers thereof, e.g., ethylenevinylacetate copolymer, etc. Alsoincluded are natural and synthetic rubbers, e.g., diene polymers such aspolyisoprene (natural or synthetic), or polybutadiene (solution oremulsion prepared); copolymers of dienes with copolymerizablemonoethyleneically unsaturated monomers such as styrene, alphamethylstyrene, acrylonitrile, isobutylene, vinyl pyridine, acrylic acid,acrylates, ethylene, propylene, etc. such as butadiene-styrenecopolymer, butadiene-acrylonitrile copolymer, and isobutylene-isoprenecopolymer. Also suitable are halogen containing hydrocarbon chainpolymers with or without plasticizers, such as polyvinylchloride, postchlorinated polyvinylchloride, chlorinated polybutadiene and the like.Suitable hydrocarbon chain polymers are described in U.S. Pat. No.3,424,821, particularly column 2 thereof, incorporated herein byreference.

2. Also suitable are resinous or rubbery interpolymers having a minoramount of unsaturation, such as rubbery terpolymers of two or moredifferent alpha olefins (usually ethylene and propylene although otherpairs of monoolefins may be employed) with a small amount of at leastone copolymerizable multiolefin. Usually the multiolefin contains from 5to 22 carbon atoms and has two double bonds separated by more than twocarbon atoms. The multiolefin ordinarily comprises from about 0.5 to notgreater than about 20 mole percent of the interpolymer, and the ethyleneand propylene units are present in ratios from about 1:4 to about 3:1.Examples of suitable multiolefins are straight or branched chaindiolefins, such as those in which both double bonds are terminal as in1,4-pentadiene, 1,5-hexadiene(biallyl), 2-methyl-1,5-hexadiene,3,3-dimethyl-1,5-hexadiene, 1,7-octadiene 1,9-decadiene,1,19-eicosadiene, and the like; diolefins in which only one double bondis terminal such as 1,4-hexadiene, 1,9-octadecadiene,6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene,11-ethyl-1,11-tridecadiene, and similar compounds in which the internaldouble bond is shielded. Also suitable are the bridged-ring hydrocarbonsof similar nature including endocyclic hydrocarbons containing 7 to 10carbon atoms and two double bonds especially those containing amethylene or an ethylene bridge, for example: (a) unsaturatedderivatives of bicyclo[2.2.1] heptane containing at least two doublebonds, including bicyclo [2.2.1] hepta-2,5-diene; dicyclopentadiene(also named 3a, 4,7,7a-tetrahydro- 4,7-methanoindene),tricyclopentadiene, and tetracyclopentadiene; (b) unsaturatedderivatives of bicyclo-[2.2.2] octane containing at least two doublebonds, including bicyclo[ 2.2.2] octa-2,5-diene; (c) unsaturatedderivatives of bicyclo [3.2.1] octane containing at least two doublebonds; (d) unsaturated derivatives of bicyclo [3.3.1]-nonane containingat least two double bonds; (e) unsaturated derivatives ofbicyclo-[3.2.2]-nonane containing at least two double bonds, and thelike. Preferred are dicyclopentadiene, 1,4-hexadiene, methylenenorbornene and ethylidene norbornene.

Suitable resinous and rubbery interpolymers are described in U.S. Pat.No. 3,361,691, particularly column 1, line 37-column 2, line 3 thereof,and U.S. Pat. Nos. 3,000,866, 3,000,867, 3,063,973, 3,462,399, and3,489,801, particularly column 1, line 67-column 2, line 35, all of saidpatents being incorporated by reference herein.

3. Similarly suitable are gum plastics represented by that class ofmaterials combining plastics and rubbers. These materials, also referredto as resin-rubber blends generally comprise a mixture of a hard,relatively brittle polymer (resin) and a minor portion of a relativelysoft, rubbery polymer. Particularly well known among this group ofpolymers are the ABS (acrylonitrile-butadiene-styrene) polymers.

Suitable gum plastics which can be used with the present invention aredescribed in U.S. Pat. No. 3,489,821, particularly column 1, line52-column 4, line 34 thereof, U.S. Pat. No. 3,489,822, particularlycolumn 1, line 51-column 4, line 45 thereof, said patents beingincorporated by reference herein.

The ABS resins which best characterize the gum plastics, are made in awell known manner by interpolymerizing styrene and acrylonitrilemonomers in the presence of a rubber which is either polybutadiene or acopolymer of butadiene and styrene, said copolymer containing not morethan 10% by weight of combined styrene based on the sum of the weightsof butadiene and styrene. Polymerization systems such as emulsion, mass,or solution are also applicable for ABS preparation. The manufacture ofsuch ABS resins is shown in detail in U.S. Pat. Nos. 2,820,773,2,802,809, 3,238,275, and 3,260,772, particularly column 3, lines 32-50thereof, each of said patents being incorporated by reference herein.The ABS graft polymer-containing resins used in our invention can bemade with varying rubber content, this conveniently being achieved inaccordance with known practice (e.g., as shown in U.S. Pat. No.2,820,773) by admixing additional acrylonitrile-styrene copolymer latexof grafted material, and co-precipitating.

It is further possible to substitute for the acrylonitrile-styreneresinous portion, mixtures of styreneacrylonitrile resin and a vinylresin such as vinyl chloride polymer (particularly polyvinyl chloride).

In place of using acrylonitrile itself for the preparation of thepolymer, one may substitute for some or all of the acrylonitrile,equivalent similar monomers such as homologs or substitution products ofacrylonitrile, e.g., methacrylonitrile, ethacrylonitrile, methylacrylate, and the like.

Similarly, in place of using styrene itself in the preparation of thepolymers used in the invention, one may substitute for some or all ofthe styrene, equivalent monomers including substitution products ofstyrene, such as alkyl-substituted styrenes, including alpha-alkylstyrenes and nuclear alkyl-substituted styrenes such asalpha-methyl-styrene, other nuclear methyl-substituted styrenes, nuclearmonoethyl-substituted styrenes, the mono- and di-chloro styrenes, etc.

4. Further suitable are foamed and unfoamed rigid polyurethanes, i.e.,organic diisocyanate-modified polyesters, polyethers,polyester-polyethers and polyester-polyamides, both saturated andolefinically unsaturated. Such polymers are generally obtained from thereaction of a polyisocyanate, usually a diisocyanate, with apolyfunctional compound containing active-hydrogen groups, such ashydroxy-terminated polyesters, castor oil, polyester amides andpolyalkylene ether glycols as well as mixtures of two or more of theseclasses of polyfunctional compounds. The material used for reaction withthe polyisocyanate to make the polyurethane is frequently a polyether orpolyester glycol having a molecular weight of from 400 to 6000,preferably in the 1000-2000 range. Mention may be made of chain extendedpolyesters made from a glycol (e.g. ethylene and/or propylene glycol)and a saturated dicarboxylic acid (e.g. adipic acid). Usually thestarting glycol contains from 2 to 20 carbon atoms and the acid containsfrom 4 to 12 carbon atoms. Polyethylene adipate, polyethyleneadipate-phthalate, polyneopentyl sebacate, etc. may be mentioned. Smallamounts of tri-alcohols such as trimethylolpropane or trimethylolethanemay be included. There may also be mentioned the polyethers, such aspolypropylene glycol, polypropylene-ethylene glycol andpolytetramethylene glycol. Among the suitable polyisocyanates may bementioned m- and p-phenylene diisocyanates; toluene diisocyanate;p,p'-diphenylmethane diisocyanate; 3,3'-dimethyl (ordimethoxy)-4,4'-biphenyl diisocyanate; 1,5-naphthylene diisocyanate;p,p',p"-triphenylmethane triisocyanate; p-phenylene diisothiocyanate,etc. The isocyanate is, of course, used in an amount at least equivalentto the hydroxyl groups in the starting polymer; larger quantities ofdiisocyanate favor formation of liquid prepolymer. Generally the molarratio of diisocyanate to glycol is in the 1.2:1 to 3:1 range. Foradditional examples of (e.g., adipic starting materials for makingpolyurethanes, reference may be had to the following: Otto Bayer in"Angewandte Chemie," A/59 ( 1947), No. 9, p. 264; and U.S. Pat. No.3,105,062 incorporated herein by reference. Suitable polyurethanes aredescribed in U.S. Pat. No. 3,412,071, particularly column 5, line44-column 4, line 6 thereof, U.S. Pat. Nos. 2,734,045 and 3,457,326,each of said patents being incorporated by reference herein.

5. Also suitable are polysulfones. Such polysulfones have a basicstructure of recurring units having the formula

    --O--E--O--E'--

wherein E is the residuum of a dihydric phenol and E' is the residuum ofthe benzenoid compound having an inert electron withdrawing group in atleast one of the positions ortho and para to the valence bonds, whereboth of said residua are valently bonded to the ether oxygens througharomatic carbon atoms and wherein at least one of E or E' is dinuclearand at least one of the pair of nuclei are joined by a sulfone (--SO₂--) group.

The residuum E of the dihydric phenol can be, for instance, amononuclear phenylene group as results from hydro-quinone andresorcinol, or it may be a di- or polynuclear residuum. The residuum Ecan also be substituted with other inert nuclear substituents such ashalogen, alkyl, alkoxy and like inert substituents.

It is preferred that the dihydric phenol be a weakly acidic dinuclearphenol such as, for example, the dihydroxy diphenyl alkanes or thenuclear halogenated derivatives thereof, which are commonly known as"bisphenols," such as, for example, the2,2-bis-(4-hydroxyphenyl)propane, 1,1-bis-(4-hydroxyphenyl)-2-phenylethane, bis-(4-hydroxyphenyl)methane, orthe chlorinated derivatives containing one or two chlorines on eacharomatic ring. Other suitable dinuclear dihydric phenols are thebisphenols of a symmetrical or unsymmetrical joining group as, forexample, ether oxygen (--O--), carbonyl (--CO--), sulfide (--S--),sulfone (--SO₂ --) or hydrocarbon residue in which the two phenolicnuclei are joined to the same or different carbon atoms of the residuesuch as, for example, the bisphenol of acetophenone, the bisphenol ofbenzophenone, the bisphenol of vinyl cyclohexane, the bisphenol ofα-pinene, and the like bisphenols where the hydroxyphenyl groups arebound to the same or different carbon atoms of an organic linking group.

Such dinuclear phenols can be characterized as having the structure:##STR24## wherein Ar is an aromatic group and preferably is a phenylenegroup, Y and Y₁ can be the same or different inert substituent groups asalkyl groups having from 1 to 4 carbon atoms, halogen atoms, i.e.,fluorine, chlorine, bromine, or iodine, or alkoxy radicals having from 1to 4 carbon atoms, r and z are integers having a value of from 0 to 4,inclusive, and R is representative of a bond between aromatic carbonatoms as in dihydroxydiphenyl, or is a divalent radical, including forexample, inorganic radicals as --CO--, --O--, --S--, --S--S--, --SO₂ --,and divalent organic hydrocarbon radicals such as alkylene, alkylidene,cycloaliphatic, or the halogen, alkyl, aryl or like substitutedalkylene, alkylidene and cycloaliphatic radicals as well asalkalicyclic, alkarylene and aromatic radicals and a ring fused to bothAr group.

Examples of specific dihydric polynuclear phenols include among others:the bis-(hydroxyphenyl)alkanes such as

2,2bis(4-hydroxyphenyl)propane,

2,4'-dihydroxydiphenyl-methane,

bis-(2-hydroxyphenyl)methane,

bis-(4-hydroxyphenyl)methane,

bis-(4-hydroxy-2,6-dimethyl-3-methoxyphenyl)methane,

1,1-bis-(4-hydroxyphenyl)ethane,

1,2-bis-(4-hydroxyphenyl)ethane,

1,1-bis-(4-hydroxy-2-chlorophenyl)ethane,

1,1-bis-(3-methyl-4-hydroxyphenyl)propane,

1,3-bis-(3-methyl-4-hydroxyphenyl)propane,

2,2-bis-(3-phenyl-4-hydroxyphenyl)propane,

2,2-bis-(3-isopropyl-4-hydroxyphenyl)propane,

2,2-bis-(2-isopropyl-4-hydroxyphenyl)propane,

2,2-bis-(4-hydroxynaphthyl)propane,

2,2-bis-(4-hydroxyphenyl)pentane,

3,3-bis-(4-hydroxyphenyl)pentane,

2,2-bis-(4-hydroxyphenyl)heptane,

bis-(4-hydroxyphenyl)phenylmethane,

2,2-bis-(4-hydroxyphenyl)-1-phenylpropane,

2,2-bis-(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the like;

Di(hydroxyphenyl)sulfones such as bis-(4-hydroxyphenyl)-sulfone,2,4'-dihydroxydiphenyl sulfone, 5'-chloro-2,4'-dihydroxydiphenylsulfone, 5'-chloro-4,4'-dihydroxydiphenyl sulfone, and the like;

Di(hydroxyphenyl)ethers such as bis-(4-hydroxyphenyl)-ether, the 4,3'-,4,2'-, 2,2'-, 2,3'-dihydroxydiphenyl ethers,4,4'-dihydroxy-2,6-dimethyldiphenyl ether,bis-(4-hydroxy-3-isobutylphenyl)ether,bis-(4-hydroxy-3-isopropylphenyl)ether,bis-(4-hydroxy-3-chlorophenyl)-ether,bis-(4-hydroxy-3-fluorophenyl)ether, bis-(4-hydroxy-3-bromophenyl)ether,bis-(4-hydroxynaphthyl)-ether, bis-(4-hydroxy-3-chloronaphthyl)ether,4,4'-dihydroxy-3,6-dimethoxydiphenyl ether,4,4'-dihydroxy-2,5-diethoxydiphenyl ether, and like materials.

It is also contemplated to use a mixture of two or more differentdihydric phenols to accomplish the same ends as above. Thus, whenreferred to above, the E residuum in the polymer structure can actuallybe the same or different aromatic residua.

As used herein, the E term defined as being the "residuum of thedihydric phenol" refers to the residue of the dihydric phenol after theremoval of the two aromatic hydroxy groups. Thus, it is readily seenthat polyarylene polyethers contain recurring groups of the residuum ofthe dihydric phenol and the residuum of the benzenoid compound bondedthrough aromatic ether oxygen atoms.

The residuum E' of the benzenoid compound can be from anydihalobenzenoid compound or mixture of di-halobenzenoid compounds whichcompound or compounds have the two halogens bonded to benzene ringshaving an electron withdrawing group in at least one of the positionsortho and para to the halogen group. The dihalobenzenoid compound can beeither mononuclear where the halogens are attached to the same benzenoidring or polynuclear where they are attached to different benzenoidrings, as long as there is the activating electron withdrawing group inthe ortho or para position of that benzenoid nucleus.

Any of the halogens may be the reactive halogen substituents on thebenzenoid compounds, fluorine and chlorine substituted benzenoidreactants being preferred.

Any electron withdrawing group can be employed as the activator group inthe dihalobenzenoid compounds. Preferred are the strong activatinggroups such as the sulfone group (--SO₂ --) bonding two halogensubstituted benzenoid nuclei as in the 4,4'-dichlorodiphenyl sulfone and4,4'-difluorodiphenyl sulfone, although such other strong withdrawinggroups hereinafter mentioned can also be used with ease. It is furtherpreferred that the ring contain no electron supply groups on the samebenzenoid nucleus as the halogen; however, the presence of other groupson the nucleus or in the residuum of the compound can be tolerated.Preferably, all of the substituents on the benzenoid nucleus are eitherhydrogen (zero electron withdrawing), or other groups having a positivesigma value, as set forth in J. F. Bunnett in Chem. Rev., 49,273 (1951)and Quart. Rev., 12,1 (1958).

The electron withdrawing group of the dihalobenzenoid compound canfunction either through the resonance of the aromatic ring, as indicatedby those groups having a high sigma value, i.e. above about +0.7 or byinduction as in perfluro compounds and like electron sinks.

Preferably the activating groups should have a high sigma value,preferably above 1.0, although sufficient activity is evidenced in thosegroups having a sigma value above 0.7.

The activating group can be basically either of two types:

a. monovalent groups that activate one or more halogens on the same ringas a nitro group, phenylsulfone, or alkylsulfone, cyano,trifluoromethyl, nitroso, and hetero nitrogen as in pyridine.

b. divalent groups which can activate displacement of halogens on twodifferent rings, such as the sulfone group --SO₂ --; the carbonyl group--CO--; the vinyl group --CH=CH--; the sulfoxide group --SO--; the azogroup --N=N--; the saturated fluorocarbon group

    --CF.sub.2 CF.sub.2 --;

organic phosphine oxides ##STR25## where R is a hydrocarbon group; andthe ethylidene group ##STR26## where X can be hydrogen or halogen ordivalent groups which can activate halogens on the same ring such aswith diflurobenzoquinone, 1,4- or 1,5- or 1,8-difluoroanthraquinone.

If desired, the polymers may be made with mixtures of two or moredihalobenzenoid compounds each of which has this structure, and whichmay have different electron withdrawing groups. Thus, the E' residuum ofthe benzenoid compounds in the polymer structure may be the same ordifferent.

It is seen also that as used herein, the E' term defined as being the"residuum of the benzenoid compound" refers to the aromatic or benzenoidresidue of the compound after the removal of the halogen atoms on thebenzenoid nucleus. Suitable polysulfones are described in U.S. Pat. No.3,365,517, particularly columns 2-6 thereof, incorporated by referenceherein.

6. Also suitable are epoxy resins formed from polyepoxides and an epoxycuring agent. The polyepoxide may be any material having more than oneepoxy group, i.e., more than one ##STR27## group, an epoxy equivalencyper 100 grams greater than 0.20 as determined by standard analysis, andpreferably a molecular weight below 900. These polyepoxides may besaturated or unsaturated and aliphatic, cycloaliphatic and aromatic andmay be substituted with substituents, such as chlorine atoms, hydroxylgroups, alkoxy radicals and the like.

Examples of these polyepoxides include, among others, vinyl cyclohexenedioxide, 2,3,5,6-diepoxyoctane, 2,3,6,7-diepoxydodecane,1,2-epoxy-3-(2,3-epoxypropyl)cyclohexane,1,2-epoxy-4-epoxybutyl)cyclohexane, epoxidized triglycerides such asepoxidized glycerol trioleate and epoxidized glycerol trilinoleate, themonoacetate of epoxidized glycerol dioleatebis(2,3-epoxycyclopentyl)ether, and the like.

Other polyepoxides comprise the polyepoxy polyethers obtained byreacting, preferably in the presence of an acid-acting compound, such ashydrofluoric acid, one of the aforedescribed halogen-containing epoxideswith a polyhydric alcohol, and subsequently treating the resultingproduct with an alkaline component. As used herein and in the claims,the expression "polyhydric alcohol" is meant to include those compoundshaving at least two free alcoholic OH groups and includes the polyhydricalcohols and their ethers and esters, hydroxy-aldehydes,hydroxy-ketones, halogenated polyhydric alcohols and the like.

Polyhydric alcohols that may be used for this purpose may be exemplifiedby glycerol, propylene glycol, ethylene glycol, diethylene glycol,butylene glycol, hexanetriol, sorbitol, mannitol, pentaerythritol,polyallyl alcohol, polyvinyl alcohol, inositol, trimethylolpropane,bis(4-hydroxycyclohexyl)dimethylmethane, 1,4-dimethylolbenzene,4,4'-dimethyloldiphenyl, dimethyloltoluenes, and the like. Thepolyhydric ether alcohols include, among others, diglycerol,triglycerol, dipentaerythritol, tripentaerythritol, dimethylolanisoles,beta-hydroxyethyl ethers of polyhydric alcohols, such as diethyleneglycol, polyethylene glycols, bis(beta-hydroxyethyl ether) ofbis-phenol, betahydroxyethyl ethers of glycerol, pentaerythritol,sorbitol, mannitol, etc., condensates of alkylene oxides, such asethylene oxide, propylene oxide, butylene oxide, isobutylene oxide,glycidyl, epichlorohydrin, glycidyl ethers, etc., with polyhydricalcohols, such as the foregoing and with polyhydric thioesters, such as2,2'-dihydroxy diethyl sulfide, 2,2'-3,3'-tetrahydroxy dipropyl sulfide,etc. The hydroxy-aldehydes and ketones may be exemplified by dextrose,fructose, maltose, glyceraldehyde. The mercapto (thio) alcohols may beexemplified by alpha-monothioglycerol, alpha, alpha-dithioglycerol, etc.The polyhydric alcohol esters may be exemplified by monoglycerides, suchas monostearin, monoesters of pentaerythritol and acetic acid, butyricacid, pentanoic acid, and the like. The halogenated polyhydric alcoholsmay be exemplified by the monochloride of pentaerythritol, monochlorideof sorbitol, monochloride of mannitol, monochloride of glycerol, and thelike.

Coming under special consideration are the polyglycidyl polyethers ofpolyhydric alcohols obtained by reacting the polyhydric alcohol withepichlorohydrin, preferably in the presence of 0.1% to 5% by weight ofan acid-acting compound, such as boron trifluoride, hydrofluoric acid,stannic chloride or stannic acid. This reaction is effected at about 50°to 125° C with the proportions of reactants being such that there isabout one mole of epichlorohydrin for every equivalent of hydroxyl groupin the polyhydric alcohol. The resulting chlorohydrin ether is thendehydrochlorinated by heating at about 50° to 125° C with a small, e.g.,10% stoichiometrical excess of a base, such as sodium aluminate.

The products obtained by the method shown in the preceding paragraph maybe described as polyether polyepoxide reaction products which in generalcontain at least three non-cyclic ether (--O--) linkages, terminalepoxide-containing ether ##STR28## groups and halogen attached to acarbon of an intermediate ##STR29## group.

These halogen-containing polyether polyepoxide reaction productsobtainable by partial dehydrohalogenation of polyhalohydrin alcohols maybe considered to have the following general formula ##STR30## in which Ris the residue of the polyhydric alcohol which may contain unreactedhydroxyl group, Y indicates one or more of the epoxy ether groupsattached to the alcohol residue, y may be one or may vary in differentreaction products of the reaction mixture from zero to more than one,and Z is one or more, and X+Z, in the case of products derived frompolyhydric alcohols containing three or more hydroxyl groups, averagesaround two or more so that the reaction product contains on the averagetwo or more than two terminal epoxide groups per molecule.

The epoxy curing agent employed in the impregnating solution may be anyalkaline, neutral or acidic compound which acts to effect cure of thepolyepoxide to form an insoluble product. The epoxy curing agent ispreferably neutral or alkaline. Examples of curing agents include, amongothers, alkalies like sodium or potassium hydroxides; alkali phenoxideslike sodium phenoxide; carboxylic acids or anhydrides, such as formicacid, oxalic acid or phthalic anhydride; Friedel-Crafts metal halideslike aluminum chloride, zinc chloride, ferric chloride or borontrifluoride as well as complexes thereof with ethers, acid anhydrides,ketones, diazonium salts, etc.; salts, such as zinc fluoborate,magnesium perchlorate and zinc fluosilicate; phosphoric acid and partialesters thereof including n-butyl ortho-phosphate, diethylortho-phosphate and hexethyl tetraphosphate, amino compounds, such as,for example, diethylene triamine, triethylene tetraamine, dicyandiamide,melamine, pyridine, cyclohexylamine, benzyldimethylamine, benzylamine,diethylaniline, triethanolamine, piperidine, tetramethyl piperazine,N,N-dibutyl-1,3-propane diamine, N,N-diethyl-1,3-propane diamine,1,2-diamino-2-methylpropane, 2,3diamino-2-methylbutane,2,4-diamino-2-methylpentane, 2-diamino-2,6-dimethyloctane, dibutylamine,dioctylamine, dinonylamine, distearylamine, diallylamine, dioleylamine,dicyclohexylamine, methylethylamine, ethylcyclohexylamine,o-tolylnaphthylamine, pyrrolidine, 2-methylpyrrolidine,tetrahydropyridine, 2-methylpiperidine, 2,6-dimethylpiperidine,diaminopyridine, tetraethylene pentamine, metaphenylene diamine, and thelike; and soluble adducts of amines and polyepoxides and their salts,such as described in U.S. Pat. No. 2,651,589 and U.S. Pat. No. 2,640,037incorporated herein by reference.

Preferred curing agents include the alkaline or neutral materials andmore preferably the amine, polyepoxide amine adducts or their neutralsalts. Coming under special consideration are the mono- and polyamines,such as those of the formulae ##STR31## wherein R is a monovalenthydrocarbon radical and R₁ is a bivalent hydrocarbon radical containingno more than 18 carbon atoms and n is an integer, preferably from 1 to8. Particularly preferred are the aliphatic polyamines having amolecular weight below 250.

Suitable polyepoxides are described in U.S. Pat. No. 2,902,398,incorporated herein by reference.

7. Also suitable are both thermoplastic and thermosetting polyesters.Suitable thermoplastic polyesters are condensation polymers of dihydricalcohols with organo-dibasic acids, particularly dicarboxylic acids, andself-condensation polymers of omega-hydroxy carboxylic acids, thepreferred materials being poly(ethylene terephthalate), poly(ethyleneterephthalate-isophthalate), and poly(1,4-cyclohexylenedimethyleneterephthalate). Applicable are all film- and fiber-forming polyesters,in which the ester linkages are intralinear, including poly(alkylenealkanedioates), poly(cycloalkylenedimethylene alkanedioates),poly(alkylene arenedioates), poly(cycloalkylenedimethylenearenedioates), and analogous materials. Examples of the above-namedpolyesters are respectively, poly(ethylene adipate),poly(1,4-cyclohexylenedimethylene adipate), poly(ethyleneterephthalate), and poly(1,4-cyclohexylenedimethylene terephthalate).Suitable thermoplastic polyesters are described in U.S. Pat. No.3,410,749, incorporated herein by reference.

7a. The thermosetting polyesters are mixtures of unsaturated polyesterresins with copolymerizable ethylenically unsaturated monomers. Underthe influence of various catalytic or promoting substances, theseresinous compositions, which are intially liquid, or dough-likematerials can be converted into solid, insoluble and infusible shapes.This transformation is essentially a copolymerization of the unsaturatedpolyester with the added monomer, leading to a cross-linked polymer ofexceedingly high molecular weight.

The unsaturated polyester resin may be defined as a self-condensationproduct of an ester of a polyhydric alcohol with a polycarboxylic acid,at least one of which is unsaturated. Frequently the unsaturatedpolyester is made from one or more glycols and one or more alpha,beta-ethylenically unsaturated polycarboxylic acids. By way ofnon-limiting example, it may be mentioned that polyesters can beprepared from such acids as maleic, fumaric, aconitic, mesaconic,citraconic, ethylmaleic, pyrocinchoninic, veronic, or itaconic acid(with or without such acids as adipic, succinic, sebacic, phthalic,etc., or such acids as linolenic, linoleic, elaeosteric, etc.) with suchglycols as ethylene, diethylene, triethylene, polyethylene,1,3-propylene, 1,2-propylene, dipropylene (1,3 or 1,2), butylene orstyrene glycol.

The copolymerizable ethylenically unsaturated monomers suitable formixing with the foregoing unsaturated polyesters to produce the desiredthermosetting composition are also well-known. Among the more importantof such monomers may be mentioned styrene, vinyl toluene, methylmethacrylate, vinyl acetate, diallyl phthalate and triallyl cyanurate.Suitable thermosetting polyesters are described in U.S. Pat. No.3,267,055, incorporated herein by reference.

8. Further suitable polymers are polycarbonates which may be prepared byreacting a dihydric phenol with a carbonate precursor such as phosqene,a haloformate, or a carbonate ester. Generally speaking, such carbonatepolymers can be typified recurring structural units of the formula##STR32## where B is a divalent aromatic radical of the dihydric phenolemployed in the polymer producing reaction. The dihydric phenols whichmay be employed to provide such aromatic carbonate polymers aremononuclear or polynuclear aromatic compounds, containing as functionalgroups, 2 hydroxy radicals, each of which is attached directly to acarbon atom of an aromatic nucleus.

Typical dihydric phenols are

2,2-bis-(4-hydroxyphenyl)propane,

hydroquinone,

resorcinol,

2,2-bis-(4-hydroxyphenyl) pentane,

2,4-dihydroxy diphenyl methane,

bis-(2-hydroxyphenyl)methane,

bis-(4-hydroxyphenyl)methane,

bis-(4-hydroxy-5-nitrophenyl)methane,

1,1-bis-(4-hydroxyphenyl)ethane,

3,3-bis-(4-hydroxyphenyl)pentane,

2,2'-dihydroxydiphenyl,

2,6-dihydroxy naphthalene,

bis-(4-hydroxyphenyl)sulfone,

2,4'-dihydroxydiphenyl sulfone,

5'-chloro-2,4'-dihydroxydiphenyl sulfone,

bis-(4-hydroxyphenyl)diphenyl disulfone,

4,4'-dihydroxyphenyl ether,

4,4'-dihydroxy-3,3'-dichlorodiphenyl ether, and

4,4'-dihydroxy-2,5-diethoxydiphenyl ether.

A variety of additional dihydrophenols which may be employed to providesuch carbonate polymers are disclosed in U.S. Pat. No. 2,999,835. It is,of course, possible to employ two or more different dihydric phenols, ora dihydric phenol in combination with a glycol, a hydroxy terminatedpolyester, or a dibasic acid in the event a carbonate copolymer ratherthan a homopolymer is desired for use in the preparation of the mixturesof the invention.

When a carbonate ester is used as the carbonate precursor in the polymerforming reaction, the materials are reacted at temperatures of from 100°C. or higher for times varying from 1 to 15 hours. Under such conditionsester interchange occurs between the carbonate ester and the dihydricphenol used. The ester interchange is advantageously consummated atreduced pressures of the order of from about 10 to about 100 mm. ofmercury, preferably in an inert atmosphere, such as nitrogen or argon,for example.

Although the polymer forming reaction may be conducted in the absence ofa catalyst, one may, if desired, employ the usual ester exchangecatalysts, such as, for example, metallic lithium, potassium, calciumand magnesium. Additional catalysts and variations in the exchangemethods are discussed in Groggins, Unit Processes in Organic Synthesis(4th edition, McGraw-Hill Book Company, 1952), pages 616 to 620. Theamount of such catalyst, if used, is usually small, ranging from about0.001 to about 0.1%, based on the moles of the dihydric phenol employed.

The carbonate ester useful in this connection may be aliphatic oraromatic in nature, although aromatic esters, such as diphenylcarbonate, are preferred. Additional examples of carbonate esters whichmay be used are dimethyl carbonate, diethyl carbonate, phenyl methylcarbonate, phenyltolyl carbonate and di(tolyl) carbonate. Suitablepolycarbonates are described in U.S. Pat. No. 3,365,517, particularlycolumns 6 and 7.

9. Additionally suitable are cellulose esters and nitrocellulose basedcoatings including cellulose acetate, cellulose acetate propionate,cellulose acetate butyrate, ethyl cellulose, cellulose nitrate, etc.Cellulose acetate esters are prepared by the reaction of chemicalcellulose with acetic acid and acetic anhydride, sulfuric acid generallybeing used as a catalyst. Ethyl cellulose is an ether and manufacturedby the reaction of chemical cellulose with caustic to form alkalicellulose, which then reacts with ethyl chloride to form ethylcellulose. Cellulose nitrate is also referred to as nitrocellulose andis prepared by the nitration of chemical cellulose, using sulfuric acidas catalyst and dehydrating agent,

10. Formaldehyde resins, for example, phenol formaldehyde resins andurea-formaldehyde resins as described in The Encyclopedia of PolymerScience and Technology, Interscience, 1969 Edition, Volume 10, pages1-73 and Volume 2, pages 25-42, respectively.

11. Polyamides -- including polyaminated derivatives of carboxylicacids, the structural units being connected by amide or thioamidegroupings having the general formula: ##STR33## wherein X is O or S.

Such polyamides are generally formed by the reaction of dicarboxylicacids with diamines, such as, adipic acid and hexamethylene diamine,from omega-amino acids, or by a ring opening reaction of lactams such asepsilon-caprolactam. Other suitable fiber forming polyamides aredescribed in U.S. Pat. Nos. 2,071,250, 2,071,253, 1,130,523 and2,130,948, incorporated herein by reference.

Normally, the amount of fire retardant used depends on the nature of thepolymer and the proposed end use. It is thus well within the knowledgeof the skilled art worker to select the optimum content of the fireretardant system of the present invention for any given polymer.Generally, however, the amount of fire retardant is sufficient toproduce a halogen content in the polymer of preferably from about 1 to20 percent by weight of the composition and most preferably from about 2to 13 percent by weight of the composition.

EXAMPLE 1 Preparation of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione

A mixture of 54.6 g. (0.2 mole) of hexachlorocyclopentadiene, 21.6 g.(0.2 mole) of p-benzoquinone, and 10 ml. of toluene were placed in a 125ml. round bottom flask and heated for three hours so that the toluenerefluxed gently. At the end of this period the reaction mixture suddenlysolidified completely, indicating completion of the reaction. The crudeproduct was bright yellow. The damp material was transferred to aBuchner funnel, rinsed with absolute ethanol, dried on the funnel, andcrystallized from ethanol. 49 g. of bright yellow dense crystals wereobtained, m.p. 189°-193° C (reported 188° C). The yield was 64%.

The product has the following structure: ##STR34##

EXAMPLE 2 Preparation of 1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol

50 g. of the dione prepared according to Example 1 were dissolved in 300ml. of methanol and 3 g. of pyridine were added. The mixture wasrefluxed until the yellow color disappeared (about 5 hours). Uponcooling to 5°-7° C, white crystals separated. One recrystallization frommethanol gave white crystals, m.p. 186° C. The yield was almostquantitative.

The product has the following structure: ##STR35##

EXAMPLE 3 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-1,8-dione.

38 g. of the diol prepared according to Example 2 were dissolved in 300ml. anhydrous ether and 30 g. of anhydrous Na₂ SO₄ and 29 g. of Ag₂ Owere added to this solution. The reaction mixture was shaken on a ParrShaker until the color turned to deep orange (about 20 minutes).Filtration and evaporation of the ether produced an orange coloredsolid. One recrystallization from hexane-benzene mixture gave orangecrystals, m.p. 118°-119° C. The yield was about 70 percent.

The product has the following structure: ##STR36##

EXAMPLE 4 Reaction product of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8,-dione andhydroxylamine.

19 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-dioneprepared in accordance with Example 3, were dissolved in 150 ml. of 95%ethanol and 8 g. of hydroxylamine hydrochloride were added. Then 11g. ofpotassium bicarbonate were added in small increments. A slight exothermoccurred during the potassium bicarbonate addition. After 24 hours ofstirring, the mixture was poured into cold water, and a light brownsolid was obtained. Infrared spectrum showed no carbonyl and mediumintensity absorption at 1590 cm.sup.⁻¹.

The product has the following structure: ##STR37##

EXAMPLE 5 Preparation of1,2,3,4,5,6,7,8,11,11,12,12-dodecachloro-1,4,4a, 5, 8,9a-hexahydro-1,4:5,8-dimethanoanthracene-9,10-dione.

38 g. of1,2,3,4,9,9,-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-dioneprepared in accordance with Example 3 were mixed with 30 g. ofhexachlorocyclopentadiene and 30 ml. of toluene, and refluxed for 6hours. By cooling to room temperature, yellow crystals were formed andwere washed with cold Skelly B solvent. One recrystallization frombenzene-hexane 50/50 mixed solvent gave yellow crystals, m.p. 234°-235°C.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        C        29.4%       28.94       28.96                                        H        0.3 %       0.52        0.37                                         Cl       65.3        64.07       64.25                                        ______________________________________                                    

The product has the following structure: ##STR38##

EXAMPLE 6 Preparation of1,2,3,4,5,6,7,8,11,11,12,12-dodecachloro-1,4,5,8-tetrahydro-1,4:5,8-dimethanoanthracene-9,10-diol.

49 g. of1,2,3,4,5,6,7,8,11,11,12,12-dodecachloro-1,4,4a,5,8,9a-hexahydro--dimethanoanthracene-9,10-dioneprepared in accordance with Example 5, were dissolved in methanol and afew drops of pyridine were added. When warmed to about 45° C, the yellowsolution became colorless and the isomerization was complete. Aftercooling to 5° -7° C. and filtration, white crystals were obtained. Onerecrystallization from methanol gave white crystals, m.p. 329° C.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        C        29.4%       29.6        29.7                                         H        0.3 %       0.33        0.49                                         Cl       65.3 %      64.97       64.04                                        ______________________________________                                    

The product had the following structure: ##STR39##

EXAMPLE 7 Preparation of1,2,3,4,5,6,7,8,11,11,12,12-dodecachloro-1,4,5,8,tetrahydro-1,4:5,8-dimethanoanthracene-9,10-dione.

23 g. of1,2,3,4,5,6,7,8,11,11,12,12-dodecachloro-1,4,5,8-tetrahydro-1,4:5,8-dimethanoanthracene-9,10-diol,prepared in accordance with Example 6, were dissolved in 150 ml. ofanhydrous ether. Anhydrous sodium sulfate, 10 g., and 12 g. of silveroxide were added and the mixture was shaken for two hours (Parr shaker).After filtration, the deep red ether solution was evaporated and crudered crystals were obtained. One recrystallization from 50/50benzene-Skelly B solution gave red crystals, m.p. 282° -283° C.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                        Test 1   Test 2                                               ______________________________________                                        Cl       65.5%       64.58       64.50                                        ______________________________________                                    

The product has the following structure: ##STR40##

EXAMPLE 8 preparation of6-tert-butyl-1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione.

30 g. of tert-butylhydroquinone (Eastman-Kodak) were dissolved in 200ml. of anhydrous ether and 30 g. of anhydrous sodium sulfate were added.To this mixture was added 60 g. of silver oxide in small increments. Anexothermic reaction ensued. After shaking for 20 minutes, the reactionmixture was filtered and the filtrate evaporated under the hood. Yellowcrystals of tert-butyl-p-benzoquinone were obtained melting at 55° -60°C.

Hexachlorocyclopentadiene, 40 g., and 15.4 g. oftert-butyl-p-benzoquinone were dissolved in 300 ml. of toluene andrefluxed for four hours. The solution solidified upon cooling to roomtemperature. The solid was washed with methanol and recrystallized frombenzene. Yellow crystals were obtained, melting at 124° -125° C.

    ______________________________________                                               Calculated    Observed                                                 ______________________________________                                               Cl 48.9%      48.7%                                                    ______________________________________                                    

The product has the following structure: ##STR41##

EXAMPLE 9 Reaction product of 1,2,3,4,9,9-hexachloro-1,4,a,8a-tetrahydro-1,4-methanonaphthalene-5,8,-dione and hydroxylamine.

27 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared in accordance with Example 1, and 12 g. of hydroxylaminehydrochloride were dissolved in 200 ml. of dimethylsulfoxide, 5 ml. ofwater were added and then 13 g. of sodium bicarbonate were added insmall increments. The reaction mixture exothermed to 40° C. After onehour, the reaction mixture turned almost white. On pouring this solutioninto cold water, a pale yellow precipitate was obtained. Onerecrystallization from methanol gave pale yellow crystals, m.p. 157°-159° C. The infrared spectrum showed no carbonyl and weak absorption at1610 cm⁻ ¹ which may be assigned as a C=N bond.

The product has the following structure: ##STR42##

EXAMPLE 10 Preparation of6-(p-chlorophenylsulfonyl)-1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-1,8-dione,prepared as in Example 3, were dissolved in 200 ml. of benzene and 20 g.of freshly generated p-chlorobenzenesulfonyl chloride were added. Thismixture was refluxed until the orange color disappeared completely (5hours) and a white precipitate formed. The white solid was filtered offwhile hot and was recrystallized from benzene yielding white crystals,m.p. 211° -212° C.

    ______________________________________                                               Calculated    Observed                                                 ______________________________________                                               Cl 44.6%      Cl 44.8%                                                        S  5.7%       S 5.4%                                                   ______________________________________                                    

This reaction was repeated using ethanol rather than benzene as thesolvent. An identical product was obtained.

The product has the following structure: ##STR43##

EXAMPLE 11 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-6-(phenylsulfonyl)-1,4-methanonaphthalene-5,8-diol.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 3, were dissolved in 200 ml. of ethanol and 18 g.of freshly generated benzenesulfonyl chloride were added. This mixturewas refluxed for 5 hours and a white precipitate formed. The white solidwas filtered off while hot and was recrystallized from benzene yieldingwhite crystals, m.p. 215° -216° C.

    ______________________________________                                               Calculated    Observed                                                 ______________________________________                                               Cl 42.3%      42.3%                                                           S  6.2%       6.1%                                                     ______________________________________                                    

The product has the following structure: ##STR44##

EXAMPLE 12 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-5,8-dihydroxy-1,4-methanonaphth-6-ylmethyl ketone.

76 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared according to Example 2, were suspended in 100 ml. of aceticacid and then 20 ml. of boron trifluoride-diethyl ether complex wereadded. This mixture was heated at 100° -105° C for 5 hours. After beingcooled to 40° C, the mixture was poured into ice water. After repeatedrecrystallization from benzene white crystals were obtained, m.p. 135°-140° C.

Nmr showed one aromatic proton at 664 Hz as a singlet, two --OH protonsat 601 and 583 Hz as a singlet, and three acetyl protons at 226 Hz as asinglet. Infrared spectrum showed a strong phenolic --OH group and thecarbonyl at 1750 cm⁻ ¹.

    ______________________________________                                               Calculated    Observed                                                 ______________________________________                                               C 36.8%       35.7%                                                           H  1.39       1.39                                                            Cl  50.3      49.2                                                     ______________________________________                                    

The product has the following structure: ##STR45##

EXAMPLE 13 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-8-hydroxy-1,4-methanonaphth-5-yl-diethylphosphate.

19 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-dione,prepared according to Example 3, and 14 g. of diethylphosphite weremixed and 50 ml. of a methanol solution, which contained 2 g. of CH₃ONa, were added slowly under nitrogen atmosphere. An exothermic reactiontook place. After completing the addition, the reaction mixture washeated at 80° -90° C for 5 hours and then cooled to room temperature anda slight excess of acetic acid was added to neutralize the base. Thereaction mixture was poured into 300 ml. of benzene and washed withwater twice and dried over MgSO₄. Evaporation of the benzene yielded abrown colored solid. This solid was repeatedly recrystallized frommethanol yielding white crystals, m.p. 206° -208° C. The yield was about30%.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        Cl       41.2%       42.10%      41.75%                                       ______________________________________                                    

The product has the following structure: ##STR46##

EXAMPLE 14 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-8-methoxy-1,4-methanonaphth-5-yl-dimethylphosphate.

20 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 3, were dissolved in 80 ml. of dried benzene and14 g. of distilled trimethyl- phosphate were added slowly (exothermic)to the solution so that the temperature was maintained at about 50° C.When the addition was completed, the mixture turned dark but then turnedyellow after 30 minutes of additional stirring. When benzene solvent wasevaporated, a pale yellow solid was obtained. One recrystallization frombenzene-Skelly B (50/50) mix-solvent gave white crystals, m.p. 149°-150°C. Infrared showed no hydroxyl or carbonyl group.

Nmr spectrum showed three methoxy protons at 394 Hz and six methoxyprotons at 383 Hz. The total yield was about 65%.

    ______________________________________                                        Calculated               Observed                                             ______________________________________                                        Cl       42.3%               Cl  42.5%                                        P        6.16                P   6.35                                         ______________________________________                                    

The product has the following structure: ##STR47##

EXAMPLE 15 Preparation of1,2,3,4,9,9-hexachloro-5,8-diethoxy-1,4-dihydro-1,4-methanonaphthalene.

18 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, and 8 g. of NaOH were mixed in 200 ml. ofdistilled water. The diol dissolved readily, forming the sodium salt.While stirring, an excess of ethylbromide was added and stirring wascontinued for 24 hours. A white precipitate was filtered off. Onerecrystallization from methanol resulted in white crystals, m.p.161°-162° C (yield about 60%). Infrared analysis showed no carbonyl orhydroxyl group.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        Cl       48.9%       49.3%       49.0%                                        ______________________________________                                    

The product has the following structure: ##STR48##

EXAMPLE 16 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylene acetate.

20 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, were mixed with 25 g. of acetic anhydride andcooled by a water bath and then one drop of concentrated H₂ SO₄ wasadded. The reaction was exothermic and the reaction mixture instantlysolidified. One recrystallization from benzene/methanol mixture gavewhite crystals, m.p. 252°-253° C. The yield was essentiallyquantitative. Infrared analysis showed ester carbonyl and no hydroxylgroup.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        Cl       45.9%       46.23       45.98%                                       ______________________________________                                    

The product has the following structure: ##STR49##

EXAMPLE 17 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylenepropionate.

80 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared in accordance with Example 2, were mixed with 80 g. ofpropionic anhydride and then a few drops of concentrated H₂ SO₄ wereadded. As soon as the H₂ SO₄ was added the mixture solidified. The thusformed white solid was filtered from excess propionic anhydride on aBuchner funnel and washed twice with water on the funnel. This solid wasrecrystallized from benzene and white needlelike crystals were obtained,m.p. 204°-205° C. The yield was almost quantitative.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        Cl       43.2%       42.90       42.88%                                       ______________________________________                                    

The product has the following structure: ##STR50##

EXAMPLE 18 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylenedecanoate.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, were dissolved in 150 ml. of dried benzene and38 g. of decanoyl chloride were added slowly under nitrogen atmosphere.The reaction mixture was heated at 70°-75° C. until HCl evolutionceased. After cooling to room temperature, the benzene was evaporatedunder vacuum and a liquid product was obtained.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        Cl       31.7%       29.98       30.06                                        ______________________________________                                    

The product has the following structure: ##STR51##

EXAMPLE 19 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylene pivalate.

To a mixture of 38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, and 16 g of pyridine in 200 ml. of drybenzene, 24 g. of pivaloyl chloride were added from a dropping funnel.After four hours heating at 60°-70° C. the mixture was cooled to roomtemperature and the white pyridinium salt was filtered off. Evaporationof the benzene resulted in a white solid. This solid was recrystallizedfrom benzene-Skelly "B" mixed solvent yielding white crystals, m.p.134°-135° C.

    ______________________________________                                        Calculated             Observed                                               ______________________________________                                        Cl       38.7%                 38.9%                                          ______________________________________                                    

The product has the following structure: ##STR52##

EXAMPLE 20 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-naphth-5,8-ylene trichloroacetate.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-dimethanonaphthalene-5,8-diol,prepared as in Example 2, 16 g. of pyridine, and 200 ml. of dry benzenewere mixed, and 40 g. of trichloroacetylchloride were added slowly tothe mixture from a dropping funnel. After four hours heating at 60°-70°C., the mixture was cooled to room temperature and the white pyridiniumsalt was filtered off. Evaporation of the benzene resulted in a whitesolid. This solid was recrystallized from benzene-Skelly "B" mixedsolvent yielding white crystals, m.p. 135°-136° C. The yield was about60% after recrystallization. Nmr showed only one singlet at 718 Hz.Infrared showed carbonyl at 1790 cm.sup.⁻¹ and no --OH group. Chlorineanalysis showed:

    ______________________________________                                        Calculated             Observed                                               ______________________________________                                        Cl       63.4%             61.5%                                              ______________________________________                                    

The product has the following structure: ##STR53##

EXAMPLE 21 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,6,8-triylacetate.

20 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 3, were mixed with 20 ml. of acetic anhydride,and 3 ml. of concentrated H₂ SO₄ were added to the mixture. The mixturewas then stirred vigorously at 90° C. until the orange colordisappeared. After cooling to room temperature, the formed white solidwas filtered on a Buchner funnel and washed twice with water. This solidwas recrystallized from ethanol and white crystals were obtained, m.p.179°-180° C. Total yield was about 70%. Nmr showed 2 protons (aromatic)at 687.5 Hz, 6 protons (methyl) at 227.5 Hz, and 3 protons (methyl) at222 Hz. all as singlets. Infrared analysis showed one carbonyl at 1775cm.sup.⁻¹ and no --OH group.

    ______________________________________                                        Calculated             Observed                                               ______________________________________                                        C        39.0%             38.8                                               H        1.91              1.95                                               Cl       40.7              39.6                                               ______________________________________                                    

The product has the following structure: ##STR54##

EXAMPLE 22 Preparation of2,2'-(1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonapth-5,8-ylenedioxy)diethanol.

NaOH (10g.) was dissolved in 200 ml. of distilled water and then 38 g.of 1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared according to Example 2, were added as quickly as possible undernitrogen flow. The diol dissolved readily and then 34 g. (large excess)of chloroethanol were added and the mixture was heated at 50°-60° C. for12 hours. As the reaction proceeded, a white precipitate formed. Thiswhite solid was filtered and washed with water twice. Repeatedrecrystallization from water-methanol (50/50) mix-solvent gave whitecrystals, m.p. 150°-151° C. The yield was about 65%.

    ______________________________________                                        Calculated               Observed                                             ______________________________________                                                                   Test 1   Test 2                                    ______________________________________                                        C        38.4%             38.5     38.7%                                     H         2.6              2.59     2.68                                      Cl       45.4              44.8     44.5                                      ______________________________________                                    

The product has the following structure: ##STR55##

EXAMPLE 23 Preparation of5,8-diallyloxy-1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene.

NaOH (20 g.) was dissolved in 300 ml. of water-methanol mix solvent(200/100) and nitrogen was bubbled through the solution for 20 minutes.80 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-4,8-diol,prepared as in Example 2, were quickly added under nitrogen flow. Whilestirring, 40 g. of allylbromide were added at one time. A slightexothermic reaction was observed. This reaction mixture was heated at50°-60° for 6 hours. When cooled in an ice water bath, a dark coloredsolid was obtained. Repeated recrystallization from methanol gave whitecrystals, m.p. 114°-115° C. The yield after the recrystallization waspoor (about 30%). Nmr showed two aromatic protons at 677 Hz as asinglet, six olefinic protons at 615-519 Hz as a complicated multiplet,and four methylene protons at 452.2 - 447.5 Hz as a multiplet. Infraredanalysis showed no --OH group.

    ______________________________________                                        Elemental Analysis:                                                                              Calculated   Observed                                      ______________________________________                                               Carbon      44.2%        43.6%                                                Hydrogen    2.6          2.5                                                  Chlorine    46.2         45.5                                          ______________________________________                                    

The product has the following structure: ##STR56##

EXAMPLE 24 Preparation of1,2,3,4,9,9-heptachloro-1,4,4a8a-tetrahydro-1,4-methanonaphthalene-5,8-dione.

A mixture of 272.8 grams (1 mol) of hexachlorocyclopentadiene, 142.5grams (1 mol.) of 2-chloro-1,4-benzoquinone and 35 ml. of toluene wasstirred continuously and gradually heated to 130°-140° C. during aperiod of two hours. This temperature was maintained for five hours. Thebrown solution crystallized while at room temperature overnight. Thecrude product was recyrstallized from a mixture of 3 liters ofSkellysolve and 0.5 liter of acetone. The recrystallized product was areddish-orange, coarsely crystalline solid. The yield was 342.6 grams(82.5% of theory). M.P. 175°-177° C. The product has the followingstructure: ##STR57##

EXAMPLE 25 Preparation of1,2,3,4,6,9,9-heptachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol.Skellysolve. recrystallized 12.5°

A mixture of 256 grams (0.62 mol.) of1,2,3,4,6,9,9-heptachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared according to Example 24, and 500 ml. of methanol in a 2 literreaction flask was stirred at room temperature while air in the reactionvessel was swept out with nitrogen. Six ml. of pyridine was then addedto the liquid-solid mixture. The resulting reaction mixture wascontinuously stirred, and refluxed vigorously for 8.5 hours. Aftercooling the mixture to 0° C., it was filtered, and the crude solid waswashed with cold Skellysolve. Yield 121 grams. The product wasrecrystallized from a mixture of 1000 ml. of Skellysolve and 250 ml. ofacetone. M.P. 120.5° - 122° C. The product has the following structure:##STR58##

EXAMPLE 26 Preparation of1,2,3,4,6,9,9-heptachloro-1,4-dihydro-1,4-methanonaphth-5,8-yleneacetate.

23 g. of1,2,3,4,6,9,9,-heptachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 25, were mixed with 25 g. of acetic anhydride.The mixture was cooled in a water bath and then one drop of concentratedH₂ SO₄ was added. The reaction was exothermic and the reaction mixtureinstantly solidified. Recrystallization from benzene/methanol solventgave white crystals, m.p. 160°-162° C. The yield was essentiallyquantitative.

    ______________________________________                                        Calculated             Observed                                               ______________________________________                                        Cl       49.6%             49.1%                                              ______________________________________                                    

The product has the following structure: ##STR59##

EXAMPLE 27 Preparation of6-(p-chlorobenzenesulfonyl)-1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-yleneacetate.

30 g. of6-(p-chlorobenzenesulfonyl)-1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 10, were mixed with 40 ml. of acetic anhydrideand a few drops of concentrated H₂ SO₄ were added. As soon as the H₂ SO₄was added the reaction became exothermic and the reaction mixturesolidified. After adding 10 ml. more of acetic anhydride and shaking for10 more minutes the white solid was filtered off on a Buchner funnel.This solid was recrystallized from benzene-Skelly B mixed solventyielding white crystals, m.p. 215°-216° C.

    ______________________________________                                        Calculated             Observed                                               ______________________________________                                                                   Test 1   Test 2                                    ______________________________________                                        Cl       38.7%             38.54    38.78%                                    S        5.0               4.46     4.58                                      ______________________________________                                    

The product has the following structure: ##STR60##

EXAMPLE 28 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylenebutylcarbamate.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, were dissolved in 200 ml. of dry benzene and25 g. of n-butylisocyanate and then a few drops of triethylamine wereadded. The reaction mixture was then heated at 70°-75° C. for 3 hours.After cooling to room temperature, a white precipitate was formed andwas filtered off on a Buchner funnel. This white solid was insoluble inbenzene and melted at 201°-202° C.

    ______________________________________                                        Calculated             Observed                                               ______________________________________                                        Cl       36.8%             37.4%                                              N        4.8               4.7                                                ______________________________________                                    

The product has the following structure: ##STR61##

EXAMPLE 29 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylene diethylcarbonate,

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, were dissolved in a mixture of 200 ml. of drybenzene and 16 g. of pyridine. Then 25 g. of chloroethyl carbonate wereadded slowly. An exothermic reaction ensued. This reaction mixture washeated under gentle reflux of benzene. After 6 hours the reactionmixture was cooled to room temperature and the pyridinium salt formedwas filtered off. Evaporation of benzene resulted in a white solid. Thissolid was recrystallized from hexane-benzene mixed solvent and yieldedwhite crystals, m.p. 116°-117° C.

    ______________________________________                                        Calculated             Observed                                               ______________________________________                                        Cl       40.6%             39.9%                                              ______________________________________                                    

The product had the following structure: ##STR62##

EXAMPLE 30 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-8-hydroxy-1,4-methanonaphth-5-ylp-chlorophenylsulfonate.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-dihydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 3, were dissolved in 200 ml. of benzene and 20 g.of freshly generated p-chlorobenzenesulfinyl chloride was added. Thismixture was refluxed until the orange color disappeared completely (5hours) and a white precipitate formed. The white solid was filtered off.(See Example 10). The filtrate solution was concentrated and dissolvedin benzene-Skelly B (50/50) mixed solvent and treated with charcoal.Evaporation of the solvent gave a white solid. This solid wasrecrystallized from Skelly B-benzene (50/50) solvent yielding whitecrystals, m.p. 165° C.

    ______________________________________                                        Calculated           Observed                                                 ______________________________________                                        Cl       44.6%           Cl    44.4%                                          S         5.7            S      5.6                                           ______________________________________                                    

The product has the following structure: ##STR63##

EXAMPLE 31 Preparation of1,2,3,4,9,9-hexabromo-1,4-dihydro-1,4-methanonaphthalene-5,8-diol.

Distilled water (3.34 kg.) was placed in a 5 liter, 3-neck, round bottomflask equipped with a stirrer, condenser, thermometer, and cooling bath.Sodium hydroxide (528 g.; 13.2 moles; 100% excess) was added to thewater in portions, and the solution was stirred continuously. When theaddition was completed and the temperature of the solution was at 0° C.or slightly lower, bromine (527.4 g.; 3.3 moles; 169 ml.) was added in afairly rapid stream through a dropping funnel. The temperature of thesolution was kept at or somewhat below 0° C. during this addition ofbromine. When the addition was completed and the temperature of thehypobromite solution was -2° to -7° C., a (-15° to -5° C.) solution ofcold, freshly-distilled 1,3cyclopentadiene (33.05 g.; 0.5 mole; 41.07ml.) in 400 ml. of Skellysolve was added rapidly over a period of about5 minutes to the continuously stirred sodium hypobromite solution. Whenthis addition was completed, stirring was continued and the reactionmixture was allowed to warm to about 10° C. The mixture was transferredto a six liter separatory funnel and the layers were separated. Theaqueous layer was extracted at once with three 500 ml. portions ofSkellysolve and the combined extracts were added to the OriginalSkellysolve solution. The resulting solution was thoroughly dried overmolecular sieves, filtered, and the filtrate was placed on a steam bathto evaporate solvents. The residual, unrecrystallized1,2,3,4,5,5-hexabromo-1,3-cyclopentadiene (237.3 g.; 88% yield), afterrecrystallization from cyclohexane, melted at 87°-88° C.

A mixture of benzoquinone, 10.8 g. toluene (40 ml) and1,2,3,4,5,5-hexabromo-1,3-cyclopentadiene (60 g.) was heated to refluxtemperature and refluxed for four hours. At the end of this reactionperiod a dark solid had formed. This solid was placed on a Buchnerfunnel and washed with Skelly B solvent and a small amount of methanol.The solid was then recrystallized from benzene and white crystals wereobtained, m.p. 204°-206° C.

The product has the following structure: ##STR64##

EXAMPLE 32 Preparation of1,2,3,4,9,9-hexabromo-1,4-dihydro-1,4-methanonaphth-5,8-ylene acetate.

10 g. of1,2,3,4,9,9-hexabromo-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared according to Example 31 were mixed with 20 ml. of aceticanhydride and one drop of concentrated H₂ SO₄ was added to the mixture.An exothermic reaction ensued. This reaction mixture was stirred for 30minutes and then poured into ice water. The thus formed white solid wasfiltered off and recrystallized from benzene yielding white needlecrystals, m.p. 304°-305° C.

    ______________________________________                                        Calculated         Observed                                                   ______________________________________                                                               Test 1  Test 2                                         ______________________________________                                        Br       66.9%         65.70   65.21%                                         ______________________________________                                    

The product has the following structure: ##STR65##

EXAMPLE 33 Preparation of(1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylenedioxy)diacetic acid.

76 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diolprepared as in Example 2 were dissolved in a NaOH/H₂ O solution (16g/250 ml.) and then 0.4 moles of sodium-α-chloroacetate solution (46.6g/100 ml H₂ O) was added slowly under a dry nitrogen atmosphere. Thismixture was heated at 80°-90° C. for 6 hours and then cooled to roomtemperature and acidified with dilute HCl solution. The precipitatedbrown colored solid was repeatedly recrystallized from water-methanolmixed solvent.

The product has the following structure: ##STR66##

EXAMPLE 34 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylene benzoate.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diolprepared as in Example 2, 16 g. of pyridine, and 200 ml. of dry benzenewere mixed and 28 g. of benzoyl chloride were added slowly to themixture from a dropping funnel. After four hours heating at 60° -70° C.,the mixture was cooled to room temperature and the white pyridinium saltwas filtered off. Evaporation of the benzene resulted in a white solid.This solid was recrystallized from benzene-Skelly B mixed solventyielding white crystals, m.p. 213°-215° C. The yield was about 60% afterrecrystallization.

The product has the following structure: ##STR67##

EXAMPLE 35 Preparation of1,2,3,4,9,9-hexachloro-1,4-hydro-1,4-methanonaphth-5,8-ylenemethanesulfonate.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diolprepared as in Example 2 and 16 g. of pyridine were dissolved in 300 ml.of dry benzene and 22 g. of methylsulfonic chloride was added slowlyfrom a dropping funnel. After refluxing for 5 hours the mixture wascooled to -10° C. and the pyridinium salt was filtered off. The solutionwas washed twice with water and dried over anhydrous magnesium sulfate.Evaporation of benzene yielded a crude solid. This solid wasrecrystallized twice from ethanol and white crystals were obtained, m.p.184°-186° C.

    ______________________________________                                        Calculated               Observed                                             ______________________________________                                                               Test 1   Test 2                                        ______________________________________                                        Cl 39.7%               38.76    38.45                                         ______________________________________                                    

The product has the following structure: ##STR68##

EXAMPLE 36 Preparation of6-tert-butyl-1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol.

10 g. of6-tert-butyl-1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared according to Example 8, were dissolved in 50 ml. of methanol. Afew drops of pyridine were added and the solution was refluxed stronglyfor three hours. Evaporation of the methanol yielded an oily materialwhich upon recrystallization twice from Skelly B gave white needlecrystals melting at 96°-98° C.

Nmr showed nine tert.-butyl protons at 134 Hz as a singlet, two hydroxylprotons at 347 Hz and one aromatic proton at 669 Hz. Infrared spectrumshowed strong phenolic -OH group absorption at 3500 cm.sup.⁻¹ and nocarbonyl. The product has the following structure: ##STR69##

EXAMPLE 37 Preparation of 0,0'1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylenedimethylthiocarbamate.

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, and 11 g. of triethylamine were dissolved in300 ml. of dry benzene and 25 g. of dimethylthiocarbamoyl chloride wereadded slowly to the solution. After refluxing strongly for six hours thereaction mixture was cooled to room temperature and the salt wasfiltered off. The benzene solution was washed twice with water and thendried over anhydrous magnesium sulfate. Evaporation of the benzeneyielded the crude solid. This solid was recrystallized from benzene andpale yellow crystals were obtained, m.p. 195°-198° C.

The product has the following structure: ##STR70##

EXAMPLE 38 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-ylenebis(ethylene phosphite).

38 g. of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diol,prepared as in Example 2, were dissolved in 300 ml. of dry benzene and26 g. of freshly distilled chloroethylene phosphite were added slowlyfrom a dropping funnel. The reaction mixture was refluxed until no moreHCl evolved (six hours). The solvent was evaporated completely undervacuum and a pale yellow waxy material was obtained. Purification wasdifficult due to the hydrolytic nature of the compound.

The product has the following structure: ##STR71##

EXAMPLE 39 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphth-5,8-yleneo,o'-hydroxybenzoate.

A mixture of1,2,3,4,9,9-hexachloro-1,4-dihydro-1,4-methanonaphthalene-5,8-diolprepared according to Example 2 (10.0g.), salicyclic acid (7.4 g.), andphosphorus pentachloride (3.6 g.), was heated in refluxing xylene fortwo days. The crystals which formed upon cooling the reaction mixturewere separated by filtration. The crude product was recrystallized frombenzenepetroleum ether to give a pure sample, m.p. 232°-233° C.Additional product was obtained by removal of the solvent andrecrystallization of the residue from benzene-petroleum ether. Totalyield was about 27%.

    ______________________________________                                        Calculated               Observed                                             ______________________________________                                                                   Test 1   Test 2                                    ______________________________________                                        C        48.3%             48.40    48.42%                                    H         1.94              2.14     2.29                                     ______________________________________                                    

The compound has the following structure: ##STR72##

EXAMPLE 40 Preparation of1,2,3,4,9,9-hexachloro-1,4,4a,6,7,8a-hexahydro-1,4-methanonaphthalene-5,8-dione.

38 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 1, were suspended in 150 ml. of glacial aceticacid and then this mixture was poured into 20 g. of zinc dust suspendedin 150 ml. of distilled water. A slight exotherm occurred duringstirring and the temperature was maintained at 50° C. for 3 hours byexternal heating. Then 200 ml. of chloroform were added and stirring wascontinued for 30 minutes more. The chloroform layer was separated andwashed with a saturated sodium carbonate solution and dried overanhydrous magnesium sulfate. Evaporation of the chloroform left a whitesolid. One recrystallization from methanol gave white crystals, m.p.169°-170° C. Infrared spectrum showed carbonyl at 1740 cm⁻ ¹. The nmrindicated two bridgehead protons at 431 Hz (singlet) and four α- protonsat 303 Hz and 245 Hz (as a multiplet).

    ______________________________________                                        Calculated         Observed                                                   ______________________________________                                                         Test 1   Test 2                                              ______________________________________                                        C        34.5%         35.30      35.26                                       H         1.6           1.63       1.79                                       Cl       55.6          54.89      54.36                                       ______________________________________                                    

The product has the following structure: ##STR73##

EXAMPLE 41 Preparation of1,2,3,4,9,9-hexachloro-1,4,4a,6,7,8a-hexahydro-6-phenylsulfonyl-1,4-methanonaphthalene-5,8-dione.

38 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 1, were dissolved in 250 ml. of benzene, 15 g. offreshly generated benzene sulfinic acid were added and then a few dropsof water were added. This reaction mixture was heated at 40°-45° C. for12 hours and then the benzene was evaporated. The white solid residueobtained was recrystallized from benzene twice and yielded whitecrystals, m.p. 157°-158° C. The yield was about 88%.

    ______________________________________                                        Calculated         Observed                                                   ______________________________________                                                         Test 1   Test 2                                              ______________________________________                                        Cl       40.9%         39.11      39.63%                                      S        6.1            5.74      5.80                                        ______________________________________                                    

The product has the following structure: ##STR74##

EXAMPLE 42 Preparation of6-butylthio-1,2,3,4,9,9-hexachloro-1,4,4a,6,7,8a-hexahydro-1,4-methanonaphthalene-5,8-dione.

20 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 1, were dissolved in 60 ml. of benzene and then10 g. of n-butylmercaptan and a few crystals of ferric chloride wereadded. This reaction mixture was shaken for 24 hours (Parr shaker). Whenthe benzene was evaporated a white solid was obtained. Onerecrystallization from benzene-Skelly B mixture yielded white crystals,m.p. 97°-98° C. The infrared spectrum showed strong carbonyl at 1750cm.sup.⁻¹.

    ______________________________________                                        Calculated         Observed                                                   ______________________________________                                                         Test 1   Test 2                                              ______________________________________                                        Cl       45.2%         44.84      44.52                                       ______________________________________                                    

The product has the following structure: ##STR75##

EXAMPLE 43 Preparation of1,2,3,4,9,9-hexachloro-6,7-epoxy-1,4,4a,6,7,8a-hexahydro-1,4-methanonaphthalene-5,8-dione.

38 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared according to Example 1, were added slowly to a solution of 200ml. of ethanol containing 20 ml. of 30% hydrogen peroxide and 13 g. ofsodium carbonate at such a rate that the temperature was maintained at40°-50° C. The yellow color of the dione disappeared quickly. Thesolution was then cooled to 10°-13° C. and a white precipitate formed.This solid was filtered and recrystallized from ethanol, m.p. 180°-181°C.

    ______________________________________                                        Calculated           Observed                                                 ______________________________________                                        C         33.2%           32.8%                                               H          1.0            1.15                                                Cl        53.7           52.75                                                ______________________________________                                    

The product has the following structure: ##STR76##

EXAMPLE 44 Preparation of1,2,3,4,9,9-hexachloro-1,4,4a,5,6,7,8,8a-octahydro-1,4-methanonaphthalene-5,8-diol.

38 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-dimethanonaphthalene-5,8-dione,prepared as in Example 1, were dissolved in 200 ml. of ethanol and about20% excess NaBH₄ was added over a 30 minute period in small amounts sothat the temperature was maintained below 50° C. The ethanol was thenevaporated under vacuum and the residue was chromatographed on aluminausing benzene as solvent. Evaporation of the benzene yielded a whitesolid. Fractional crystallization from benzene-hexane (50/50) solventyielded as the major product a white solid melting at 163°-168° C. Nmrand infrared spectra indicate a major part is completely reducedproduct, and a minor part is only carbonyl reduced product.

The product has the following structure: ##STR77##

EXAMPLE 45 Preparation of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-6-methyl-1,4-methanonaphthalene-5,8-dione.

To a mixture of methyl-p-benzoquinone (60 g.), andhexachlorocyclopentadiene (140 g.), was added 20 ml. of toluene. Thisreaction mixture was then heated at 130°-140° C. for 3 hours. Uponcooling to room temperature the mixture solidified. This solid waswashed with Skelly "B" solvent several times on a Buchner funnel andrecrystallized from a Skelly "B"-benzene mixed solvent (20/80). Paleyellow crystals were obtained, m.p. 163°-165° C.

The product has the following structure: ##STR78##

EXAMPLE 46 Preparation of1,2,3,4,12,12-hexachloro-1,4,4a,5,8,8a,9a,10a-octahydro-1,4:5,8-dimethanoanthracene-9,10-dione.

190 g. of the dione prepared according to Example 1 were dissolved in800 ml. of acetone and 45 g. of freshly generated cyclopentadiene wereadded slowly at room temperature. A white precipitate formed whenapproximately one-third of the cyclopentadiene had been added. Thereaction mixture was stirred for two hours after all the cyclopentadienehad been added. The white solid was filtered off and additionalprecipitation occurred when the filtrate was concentrated. The combinedyield was almost quantitative. The solid was recrystallized frombenzene/Skelly B (50/50) yielding needle like crystals, m.p. 196°-198°C. Infrared spectrum showed a carbonyl at 1710 cm.sup.⁻¹ and nmr agreedwith the proposed structure.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        Cl      47.75%       47.24%      46.78                                        ______________________________________                                    

The product has the following structure: ##STR79##

EXAMPLE 47 Preparation of1,2,3,4,11,11-hexachloro-1,4,4a,9a-tetrahydro-1,4-methanoanthracene-9,10-dione.

Hexachlorocyclopentadiene (60 g.), 1,4-naphthoquinone (31.6 g.), and 30ml. of toluene were mixed, heated to reflux temperature, and maintainedat this temperature for 4 hours. After cooling to room temperature andextracting the excess hexachlorocyclopentadiene with Skelly "B" solvent,the mixture solidified slowly. This crude brown solid was recrystallizedrepeatedly from benzene/Skelly "B" mix-solvent (70/30) to yield whitecrystals, m.p. 116°-118° C.

The product has the following structure: ##STR80##

EXAMPLE 48 Preparation of1,2,3,4,9,9-hexachloro-1,4-dihydro-6-methyl-1,4-methanoaphthalene-5,8-diol

30 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-6-methyl-1,4-methanonaphthalene-5,8-dione,prepared according to Example 45, were suspended in 150 ml. of methanol.2 ml. of pyridine were added and the mixture was refluxed for 4 hours.Upon cooling in an ice-water bath, a crude white solid formed. Thissolid was recrystallized from methanol and white crystals were obtained,m.p. 159°-161° C.

The product has the following structure: ##STR81##

EXAMPLE 49 Preparation of1,2,3,4,12,12-hexachloro-1,4,4a,5,6,7,8,8a,9a,10adecahydro-1,4:5,8-dimethanoanthracene-9,10-dione.

22.5 g. of1,2,3,4,12,12-hexachloro-1,4,4a,5,8,8a,9a,10a-octahydro-1,4:5,8-dimethanoanthracene-9,10-dione,prepared as in Example 46, were dissolved in 300 ml. of ethanol and 0.5g. of Pd-C was added and shaken under 20 lbs. of hydrogen pressure on aParr Shaker. 5 lbs. of hydrogen were absorbed within 30 minutes. Thereaction mixture was filtered and upon evaporation of the ethanol awhite solid was obtained. One recrystallization from benzene/Skelly B(50/50) solvent mix gave white crystals, m.p. 190°-192° C. Infraredspectrum and nmr showed good agreement with the proposed structure.

    ______________________________________                                        Calculated        Observed                                                    ______________________________________                                                          Test 1     Test 2                                           ______________________________________                                        Cl 47.4%          47.29%     47.38%                                           ______________________________________                                    

The product has the following structure: ##STR82##

EXAMPLE 50 Preparation of1,2,3,4,11,11-hexachloro-1,4,4a,5,8,8a,9a,10a-octahydro-1,4-methano-cis(10a,8a)-anthracene-9,10-dione.

40 g. of1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8-dione,prepared as in Example 1, 200 ml. of acetone and 60 g. of 1,3-butadienewere charged in an autoclave and heated at 60°-70° C for 24 hours. Thereaction mixture was then cooled to room temperature and the acetone wasremoved by a rotary evaporator. The white solid thus obtained wasrecrystallized from benzene/Skelly B (50/50) solvent mix and whitecrystals were obtained, m.p. 185°-187° C. By further condensing thesupernatant liquid, lower melting white crystals were obtained, m.p.138°-140° C. Nmr spectra showed the higher melting solid to be the ciscompound and the lower melting solid to be the trans compound.

    ______________________________________                                        Calculated       Observed                                                     ______________________________________                                                       Test 1    Test 2                                               ______________________________________                                        Cl      49.08%       47.89%      47.66%                                       ______________________________________                                    

The product has the following structure: ##STR83##

EXAMPLE 51 Preparation of1,2,3,4,5,7,12,12-octachloro-1,4,4a,5,6,7,8,8a,9a,10a-decahydro-1,4:5,8-dimethanoanthracene-9,10-dione.

45 g. of1,2,3,4,12,12-hexachloro-1,4,4a,5,8,8a,9a,10a-octahydro-1,4:4,8-dimethanoanthracene-9,10-dione,prepared as in Example 46, were dissolved in 300 ml. of carbontetrachloride and chlorine gas was bubbled through the solution untilall solid dissolved. A white solid was obtained by evaporation of thecarbon tetrachloride. Recrystallization from benzene/Skelly B (50/50)yielded a pure product melting at 219°-221° C. Infrared spectrum and nmrshowed agreement with the proposed structure.

    ______________________________________                                        Calculated         Observed                                                   ______________________________________                                                         Test 1   Test 2                                              ______________________________________                                        Cl       54.9%         54.04%     54.13%                                      ______________________________________                                    

The product has the following structure: ##STR84##

EXAMPLE 52 2,3,4,5-Tetrachlorocyclopentadienone dimethyl acetal.

Hexachlorocyclopentadiene (818.4 g.; 3.0 moles) and methanol (500 ml.)were placed in a 3 liter, round bottom, 3-neck flask equipped withstirrer, condenser, thermometer, dropping funnel and heating mantle. Themixture was stirred continuously while a solution of potassium hydroxide(345.1 g.; 6.15 moles) in methanol (800 ml.) was added in a moderatestream during one hour. The temperature of the reaction mixture wasmaintained at 30°-38° C. by external cooling of the flask when required.After all the potassium hydroxide solution had been added thetemperature of the mixture was maintained at 33°-35° C. by very gentlyheating for 90 minutes. The reaction mixture was then filtered, and thefiltrate was brought to pH 7 by the addition of conc. hydrochloric acid(12.0 ml.). Solvent was evaporated from the neutral solution and theconcentrated filtrate was mixed with twice its volume of water, andextracted with Skellysolve three times. The combined extract was driedover molecular sieves, filtered, and freed of solvent. Distillation ofthe residual liquid under reduced pressure gave2,3,4,5-tetrachlorocyclopentadienone dimethyl acetal (522 g.; B.P. 65.5°C./0.46 mm.).

The product has the following structure: ##STR85##

EXAMPLE 53 Preparation of1,2,3,4-tetrachloro-1,4,4a,8a-tetrahydro-6,8a-dimethyl-1,4-methanonaphthalene-5,8,9-trione-9-dimethyl.acetal.

2,5-dimethoxy-p-benzoquinone (25 g.), and 52 g. (excess) of2,3,4,5-tetrachlorocyclopentadienone-dimethyl acetal prepared accordingto Example 52 were dissolved in 40 ml. of o-dichlorobenzene and refluxedovernight. After cooling to room temperature a brown solid formed. Thissolid was washed with Skelly/B on a Buchner funnel and thenrecrystallized from benzene. The thus obtained yellow solid melted at128°-130° C. The yield was about 41%.

The product has the following structure: ##STR86##

EXAMPLE 54 Preparation of5,6,7,8,9,9-hexachloro-2,3,4a,5,8,8a-hexahydro-5,8-methanonaphthal-2,3-azine-1,4-dione.

Chlorendic anhydride (37 g.) was dissolved in 150 ml. of ethanol and 10g. of hydrazine and then 10 ml. of acetic acid were added. The mixturewas heated at 80°-85° C. for 4 hours and cooled to room temperature. Thewhite solid that formed was filtered off and recrystallized fromethanol, m.p. 175°-176° C.

The product has the following structure: ##STR87##

EXAMPLE 551,2,3,4-Tetrachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8,9-trione9-dimethyl acetal.

A mixture of 2,3,4,5-tetrachlorocyclopentadienone dimethyl acetal (263.9g.; 1.0 mole), prepared according to Example 52, p-benzoquinone (108.1g.; 1.0 mole) and toluene (35.0 ml.) in a 3 liter, 3-neck, round bottomflask equipped with a stirrer, condenser, thermometer and heating mantlewas stirred continuously and heated to maintain vigorous refluxing for aperiod of 7 hours. The reaction mixture was removed from the flask whilestill liquid, and allowed to crystallize. The solid was slurried withcold methanol (2.0 liters), and the slurry was filtered. The washedsolid was dissolved in 5.5 liters of hot methanol, treated with Darcodecolorizing charcoal, filtered, and crystallized. The yield oflemon-yellow,1,2,3,4-tetrachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8,9-trione9-dimethyl acetal was 205 g.; M.P. 162°-163° C.

The product has the following structure: ##STR88##

EXAMPLE 56 Preparation of1,2,3,4-tetrachloro-1,4-dihydro-5,8-dihydroxy-1,4-methanonaphthalene-9-onedimethyl acetal.

Five hundred milliliters of methanol and 74.4 grams (0.2 mol) of1,2,3,4-tetrachloro-1,4,4a,8a-tetrahydro-1,4-methanonaphthalene-5,8,9-trione9-dimethyl acetal, prepared according to Example 55, were placed in areaction flask and the air in the flask was then swept out withnitrogen. Two milliliters of pyridine were added to the reactionmixture, which was then stirred continuously and heated sufficiently tocause vigorous refluxing. Stirring and refluxing were maintained for 51/2 hours. The reaction mixture was cooled in ice water for a short timeand then filtered. The solid was protected from light while beingair-dried on the funnel. An additional small amount of product wasobtained from the filtrate by cooling it for a short time in dry ice andfiltering. The total yield of white, finely crystalline1,2,3,4-tetrachloro-1,4-dihydro-5,8-dihydroxy-1,4-methanonaphthalene-9-onedimethyl acetal was 66.7 grams (90% of theory). M.P. 203°-204° C.

The product has the following structure: ##STR89##

EXAMPLE 57 Preparation ofendo-4a,6,7,8a-tetrachloro-1,4,4a,5,8,8a-hexahydro-1,4-methanonaphthalene-5,8-dione.

A mixture of 123 g. of chloranil, 37 g. of cyclopentadiene, 1 ml. of a50% triethylamine-methanol solution, and 400 ml. of benzene was placedin a polymerization bottle, and the bottle was capped and placed in abath heated at 65° C. for 72 hours. The adduct was isolated and purifiedby recrystallization from methanol, followed by sublimation below 100°at 1 mm. The pure adduct had a melting point of 145°-146° C.

The product has the following structure: ##STR90##

EXAMPLE 58 Preparation of1,2,3,4-tetrachloro-1,4-dihydro-9,9-dimethoxy-1,4-methanonaphth-5,8-yleneacetate.

40 g. of1,2,3,4-tetrachloro-1,4-dihydro-5,8-dihydroxy-1,4-methanonaphthalene-9-onedimethyl acetal, prepared according to Example 56 were mixed with 50 ml.of acetic anhydride and cooled by an ice bath and then a few drops ofconcentrated H₂ SO₄ were added. The reaction was exothermic and thesolution became clear. After ten minutes the solution solidified. Thecrude solid was washed on a Buchner funnel with Skelly "B"/acetone(50/50) and recrystallized from benzene/Skelly "B" (50/50) to give whitecrystals, m.p. 145°-146° C.

The product has the following structure: ##STR91##

EXAMPLE 59 Reaction product of1,2,3,4,12,12-hexachloro-1,4,4a,5,8,8a,9a,10a-octahydre-1,4:5,8-dimethanoanthracene-9,10-dioneand NaBH₄.

45 g. of1,2,3,4,12,12-hexachloro-1,4,4a,5,8,8a,9a,10a-octahydro-1,4:5,8-dimethanoanthracene-9,10-dione,prepared as in Example 46, were dissolved in 300 ml. of ethanol and 3 g.(slight excess) of NaBH₄ were added in small increments. The reactiontemperature was maintained below 40° C by external cooling. After twohours stirring, the reaction mixture was concentrated to one-third itsvolume and poured into a water-ether mixture. The ether layer wasseparated and dried. Evaporation of the ether yielded a white solid.Even though the solid was recrystallized twice from benzene/Skelly B(50/50) it still gave a broad melting point range, 205°-210° C. Infraredspectrum showed strong --OH at 0600 cm⁻ ¹ and nmr agreed reasonably wellwith a1,2,3,4,12,12-hexachloro-1,4,4a,5,8,8a,9,9a,10,10a-decahydro-1,4:58-dimethanoantracene-9,10-diol (cis/trans)structure. ##STR92##

EXAMPLE 60 Preparation of1,2,3,4,9,9-hexachloro-1,4,4a,5,6,7,8,8a-octahydro-1,4-methanonaphthalene-6-carbonitrile.

3-Cyclohexene-1-carbonitrile (Aldrich Chemical Corp.) (56 g.), and 200g. of hexachlorocyclopentadiene were mixed, heated at 160°-170° C. for 6hours, and then allowed to cool to room temperature. The reactionmixture was then vacuum distilled. Unreacted hexachlorocyclopentadienewas first removed and then the crude adduct produced was collected,175°-170° C. at 0.3 m.m. Hg. The thick liquid was crystallized veryslowly in Skelly "B". The crude solid melted at 140°-150° C.

The product has the following structure: ##STR93##

EXAMPLE 61 Preparation of1,2,3,4,7,7-hexachloro-5-(2-acetoxy-benzyl)-2-norbornene

17.6 g of freshly distilled 2-allyl acetoxy benzene and 30 g. ofhexachlorocyclopentadiene were mixed and heated at 170° - 190° C for 5hours and then the excess hexachlorocyclopentadiene was distilled off.The residue was a waxy material (pale yellow). This waxy material wasused for fire retardant tests without further purification.

The product has the following structure: ##STR94##

The following examples illustrate the fire retardant effect of variouscompounds on a number of polymers. Unless otherwise indicated the blendswere prepared by mixing the compound and polymer in a conventional tworoll mixing mill at the temperature and for the time specified. Thecompounded material was then molded to 1/8 inch thickness in a press atthe temperature and for the time specified. The molded sheets, aftercooling, were cut into strips and the strips were tested for fireretardance using the test specified.

EXAMPLES 62-137

A series of samples comprising compositions of ABS gum plasticcontaining a number of the foregoing described fire retardant compoundswere prepared by milling the fire retardant compound and the ABS plasticat 320° F for 5 minutes. Test strips were prepared and were thenevaluated for fire retardance using either ASTM method D-635,hereinafter referred to as "burn rate" and/or ASTM method D-2863,hereinafter referred to as "oxygen index". For the burn rate, the teststrips were 1/8 inch × 1/2 inch × 5 inches and for the oxygen index, thetest strips were 1/8 inch × 1/4 inch × 2 1/2 inches.

The ABS gum plastic used was a gum plastic containing 22% acrylonitrile,23% butadiene and 55% styrene.

The results of the fire retardance tests are set forth in Table 1. (Inthe tables, SE means self-extinguishing.)

                                      Table 1                                     __________________________________________________________________________    Compound                                                                            Prepared                Burn                                                  in             ABS Halogen                                                                            Rate Oxygen                                           Example                                                                             Amounts  Plastic                                                                           Content                                                                            (in/ Index                                      Example                                                                             No.   (parts)  (parts)                                                                           % wt.                                                                              min.)                                                                              %                                          __________________________________________________________________________    62    --    0        100 0    1.8  18.3                                       63    1     8.7      "   4.5  SE   --                                         64    1     11.6     "   5.8  SE   --                                         65    1     15.0     "   7.5  SE   --                                         66    2     8.7      "   4.5  1.11 --                                         67    2     11.6     "   5.8  SE   --                                         68    2     15.4     "   7.5  SE   --                                         69    2     25.0     "   11.2 SE   --                                         70    3     7.1      "   3.7  1.03 --                                         71    3     8.7      "   4.5  SE   --                                         72    3     15.4     "   7.5  SE   --                                         73    4     15.4     "   7.0  0.61 --                                         74    5     15.4     "   8.7  1.40 --                                         75    6     8.5      "   5.2  1.28 --                                         76    8     10.0     "   4.4       23.7                                       77    9     15.4     "   6.6  0.73 --                                         78    10    16       "   6.2  1.47 --                                         79    10    20       "   7.5  SE   --                                         80    11    25       "   6.2  SE   --                                         81    14    11.4     "   4.3  0.72 --                                         82    15    16       "   7.0  0.66 --                                         83    16    8.7      "   3.7  1.28 --                                         84    16    15.4     "   6.1  SE   --                                         85    16    18.5     "   7.2  SE   --                                         86    17    18.5     100 6.7  1.33                                            87    17    25       "   8.6  SE                                              88    18    20       "   5.2  1.52                                            89    18    40       "   8.9  SE                                              90    19    20       "   6.5  1.45                                            91    19    30       "   8.9  SE                                              92    20    14       "   7.8  1.71                                            93    20    16       "   8.7  SE                                              94    21    16       "   5.6  SE                                              95    22    18.4     "   7.0  SE                                              96    25    14       "   7.3  SE                                              97    26    18       "   7.6  SE                                              98    27    25       "   8.3  SE                                              99    28    24       "   7.1  1.28                                            100   29    21.5     "   7.1  SE                                              101   30    16       "   6.2  1.3                                             102   31    14.7     "   9.5  0.98                                            103   35    25       "   7.9  SE                                              104   36    10       "   4.4       23.66                                      105   37    15       "   5.0       21.64                                      106   40    18.4     "   8.1   0.8                                            107   41    18.4     "   6.0  SE                                              108   42    18.4     "    6.87                                                                              SE                                              109   43    18.4     "   8.4  SE                                              110   44    16       "   6.7  1.13                                            111   45    15.4     100 7.3  SE   --                                         112   46    15.4     "   6.4  --   24.50                                      113   46    15.4                                                                          +4.6Sb.sub.2 O.sub.3                                                                   "   6.1  SE   27.30                                      114   47    20       "   8.4  0.69 --                                         115   48    26       "   14.7 SE   --                                         116   49    20.1     "   7.9  1.21 21.20                                      117   49    15.0                                                                          +4.6Sb.sub.2 O.sub.3                                                                   "   6.0  SE   25.68                                      118   50    16.0     "   6.8  1.50 21.82                                      119   50    15.0+                                                                         3.8Sb.sub.2 O.sub.3                                                                    "   6.2  1.00 25.47                                      120   51    19.3     "   9.5  1.66 20.58                                      121   51    13.8 +                                                                        3.0Sb.sub.2 O.sub.3                                                                    "   6.4  0.99 26.91                                      122   53    25       "   7.3  1.63 --                                         123   54    15.3     "   6.3  1.5  --                                         124   54    24       "   9.1  1.45 --                                         125   56    25       "   7.7  1.97 --                                         126   57    15.4     "   6.7  1.93 --                                         127   58    30       "   7.7  1.91 --                                         128   59    19.3     "   8.2  1.45 23.45                                      129   59    12.1+                                                                         4.5Sb.sub.2 O.sub.3                                                                    "   4.9  SE   28.25                                      130   60    20       "   9.0  1.38 --                                         131   63    25       "   9.3  1.40 --                                         132   chloran 15                                                                          "        6.7 1.50 --                                              133   chloran                                                                             25       "   10.0 1.24 --                                         134   chlorendic                                                                    anhydride                                                                           15       100 7.7  1.30 --                                         135   chlorendic                                                                    anhydride                                                                           20       "   9.6  1.19 20.8                                       136   chlorendic                                                                    anhydride                                                                           25       "   11.5  .78 --                                         137   chlorendic                                                                    anhydride                                                                           30       "   13.3 --   21.4                                       __________________________________________________________________________

The fire retardant effect of the structural system of the presentinvention, i.e., the1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dione or1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dioxynucleus or a compound which is capable of being converted to the1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dionenucleus, is clearly evident from the results in Table 1. The compoundsof Examples 1-51 and 59 all possess the structural requirements of thefire retardant system of the present invention. These compounds differ,however, with respect to the ease of conversion of the 5,8-dioxy ring tothe 1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dionesystem. Thus, for example, the compounds of Examples 1, 2 and 3, havingthe structures ##STR95## respectively, are effective fire retardants atrelatively low concentration levels.

The compounds of Examples 5-8,10-12,24,25,31,36,45,47 and 48, whichcontain the required nucleus and also have additional substituents suchas alkyl, halogen, sulfonyl, etc. attached to this nucleus, are slightlyless effective than the unsubstituted compounds. Nevertheless, thesecompounds do possess significant flame retardant properties. The slightdecrease in effectiveness is most probably due to the "diluting" effectof the additional substituents. Also, the compounds of Examples 4 and 9,wherein the dione structure is in the form of an oxime, possessexcellent flame retardant properties.

In the compounds of Examples 13-23, 26-30, 32-35 and 37-39, the dioxycomponent is in the form of an ether or ester group. Such system issomewhat more difficult to convert to the1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dionesystem. Thus, these compounds, while possessing substantial fireretardant properties, are not so effective as the compounds of Examples6, 10-12,25,31,36 and 48.

Note that as the molecular weight of the ether or ester group increases,such as, for example, in the compounds of Examples 28 and 30, theeffectiveness of the compound as a fire retardant decreases, again duemost probably to "dilution".

All of the foregoing described compounds possess at least someunsaturation in the methano naphthalene ring system. If, however, the5,8-dioxy structure is present in the unbridged six membered ring in theform of either carbonyl or hydroxyl groups but the ring is completelysaturated a further slight decrease in fire retardant properties isobserved. Such a result is, of course, entirely consistent with theforegoing, inasmuch as such compounds are more difficult, in terms ofthe "activation energy" required, to convert to the1,2,3,4,9,9-hexahalo-1,4-dihydro-1,4-methanonaphthalene-5,8-dionestructure. Even so the compounds of this class, illustrated by thecompounds of Examples 40-44,46,49,50,51 and 59, do possess substantialfire retardant properties.

The compounds of Examples 53-58, 60, 61 and the known commercial fireretardants, chloran and chlorendic anhydride illustrate the criticaleffect on the fire retardant properties of a given compound ofdivergence from the structural components of the present system. Thus,compounds of Examples 53,55,56,57 and 58 do possess the 5,8-dioxynaphthalene nucleus, but do not contain a dihalomethano bridge. Thecompound of Examples 60 and chloran possess the1,2,3,4,9,9-hexahalo-1,4-dimethano naphthalene nucleus but do notcontain 5,8-dioxy substituent. In the compounds of Example 54 andchlorendic anhydride heteroatom ring systems replace the carbocyclicnaphthalene ring system. In Example 61, the hexachloro norbornene ringand the oxybenzene ring units are separated by a methylene group ratherthan being fused into the naphthalene ring system. Consequently, each ofthese compounds possesses substantially less fire retardant capabilitythan do the compounds containing the system of the present invention.

EXAMPLES 137-143

A series of samples were prepared by blending the fire retardant ofExample 2 with a natural rubber formulation. The natural rubberformulation was as follows:

    ______________________________________                                                             Parts by weight                                          ______________________________________                                        Smoked sheet           100                                                    Zinc Oxide             5                                                      Stearic Acid           2                                                      Diphenylguanidine      0.25                                                   N-cyclohexyl-2-benzothiazole-                                                 sulfonamide            0.75                                                   Sulfur                 2                                                      ______________________________________                                    

The blending was effected as follows:

A two-thirds portion of the rubber, zinc oxide and stearic acid weremixed on a warm mill (150°-160° F) for 5-8 minutes; thediphenylguanidine, N-cyclohexyl-2-benzothiazolesulfenamide, and sulfurwere then blended with the remaining one-third portion of rubber for 5-8minutes on a cool mill. The two mixtures were then combined with thefire retardant of Example 2 on a cool mill until well blended. Thecompounded stock was then cured 45 minutes at 292° F.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 2.

                  Table 2                                                         ______________________________________                                        Compound                                                                              Prepared                                                                      in                Natural                                                                              Halogen                                                                              Burn                                          Example  Amounts  Rubber Content,                                                                             Rate                                  Example No.      (parts)  (parts)                                                                              % wt.  (in/min)                              ______________________________________                                        137     2        None     110    0      2.35                                  138     2        10       110    4.7    2.05                                  139     2        15       110    6.7    1.73                                  140     2        20       110    8.6    1.16                                  141     2        25       110    10.3   SE                                    142     2        30       110    12.0   SE                                    143     2        35       110    13.5   SE                                    ______________________________________                                    

The results in Table 2 show the excellent fire retardant effect of thepresent system on the highly combustible natural rubber.

EXAMPLES 144-147

A series of samples were prepared by blending the fire retardant ofExample 2 with a butyl rubber formulation. The butyl rubber formulationwas as follows:

    ______________________________________                                                              Parts                                                   ______________________________________                                        *Butyl 218              100                                                   Zinc Oxide              5                                                     Stearic Acid            2                                                     Mercaptobenzothiazole   1.0                                                   Tet-amethyl thiuram disulfide                                                                         1.5                                                   Sulfur                  1.25                                                  ______________________________________                                         *Butyl 218 (Enjay) is a medium unsaturated copolymer of                       isobutyl-lene-isoprene having a specific gravity of 0.92 and a Mooney         viscosity, ML-3 0 260° F. of 50-60.                               

The blending was effected as follows:

Two-thirds of the rubber was mixed with the zinc oxide and stearic acidon a warm mill (150° F-160° F) for 5-8 minutes. The remaining one-thirdof the rubber was mixed with the mercaptobenzothiazole, tetramethylthiuram disulfide, and sulfur on a cool mill for 5-8 minutes. The twomixtures were then combined with the fire retardant of Example 2 on acool mill until well blended. The compounded stock was then cured 40minutes at 320° F. The samples thus prepared were burn rate and oxygenindex tested. The results of these tests are set out in Table 3.

    ______________________________________                                        Compound                                                                             Prepared                       Burn                                           in                Butyl Halogen                                                                              Rate Oxygen                                    Example  Amounts  Rubber                                                                              Content,                                                                             (in/ Index                              Example                                                                              No.      (parts)  (parts)                                                                             % wt.  min.)                                                                              %                                  ______________________________________                                        144    --       --       110.75                                                                              --     2.14 18.23                              145    2        10       "     4.6    1.63 19.01                              146    2        20       "     8.6    1.17 20.06                              147    2        30       "     11.9   1.49 22.10                              ______________________________________                                    

EXAMPLES 148-158

A series of samples were prepared by blending the fire retardant ofExample 2 of chlorendic anhydride with nylon polymers. Both "Nylon 6"nylon (Gulf) and "Zytel 63" nylon, a (du Pont) terpolymer of 6, 6:6 and6:10 were utilized.

The samples prepared from Nylon 6 were milled at 420-430° F for 4-5minutes, and molded at 430° 5 minutes.

The samples prepared from the nylon terpolymer were milled at 285° F for3 minutes and molded at 285° F for 5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 4.

                                      Table 4                                     __________________________________________________________________________    Compound                                                                           Prepared                                                                      in                 Halogen                                                    Example                                                                             Amounts                                                                            Polymer Content                                                                            Burn Rate                                        Example                                                                            No.   (parts)                                                                            (parts) % wt.                                                                              (in/min)                                         __________________________________________________________________________    148  --    --   Zytel 63 100                                                                          --   0.54                                             149  --    --   "       --   0.55                                             150  2     2.5  "       1.4  0.59                                             151  2     5.0  "       2.7  SE                                               152  2     7.5  "       3.9  Non-Burning                                      153  2     15.4 "       7.5  Non-Burning                                      154  Chlorendic                                                                          7.5  "       4.0  SE                                                    Anhydride                                                                155  Chlorendic                                                                          15.4 "       7.7  SE                                                    Anhydride                                                                156  --    --   Nylon 6 100                                                                           --   0.57                                             157  2     5.0  "       2.7  0.48                                             158  2     10.0 "       5.1  SE                                               __________________________________________________________________________

From the data in Table 4 it is clear that the system of the presentinvention is a superior fire retardant for nylon as compared with theprior art fire retardant chlorendic anhydride. Thus, whereas, in Zytelterpolymer, the chlorendic anhydride is self-extinguishing (Examples 154and 155), the system of the present invention, when used at the samelevels, renders the polymer essentially non-burning (Examples 152 and153).

EXAMPLES 159-165

A series of samples were prepared by blending the fire retardants ofExamples 2 or 3 with polymethylacrylate. The polymethylacrylate wasprepared by room temperature autopolymerization of methylacrylate.

The samples were milled at 200° F for 5 minutes and molded at 212° F.for 5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 5.

                  Table 5                                                         ______________________________________                                        Compound                                                                             Prepared                          Burn                                        in                         Halogen                                                                              Rate                                        Example  Amounts  Polymethyl-                                                                            Content,                                                                             (in/                                 Example                                                                              No.      (parts)  acrylate % wt.  min.)                                ______________________________________                                        159    --       --       100      --     1.08                                 160    2        10       100      5.1    0.02                                 161    2        15       100      7.3    0.55                                 162    2        20       100      9.3    0.56                                 163    2        25       100      11.2   0.65                                 164    3        15       100      7.3    SE                                   165    3        25       100      11.3   0.76                                 ______________________________________                                    

The results in Table 5 show the marked effect of the fire retardantsystem of the present invention on polymethylacrylate. Thus, thecompound of Example 2 markedly reduces the burn rate ofpolymethylacrylate (compare Example 159 with Examples 160-163), and thecompound of Example 3 renders the polymethylacrylate essentiallyself-extinguishing (Example 164).

EXAMPLES 166-172

A series of samples were prepared by blending the fire retardant ofExample 2 with a styrene-butadiene rubber formulation. Thestyrene-butadiene rubber formulation was as follows:

    ______________________________________                                                               Parts                                                  ______________________________________                                        *SB-R-1500               100                                                  Zinc Oxide               5                                                    Stearic Acid             2                                                    Diphenylguanidine        0.25                                                 N-cyclohexyl-2-benzothiazole                                                  sulfenamide              1.0                                                  Sulfur                   2.0                                                  ______________________________________                                         *SB-R-1500 is a cold type, emulsion polymerized styrene-butadiene             copolymer having a 22.5-24.50 wt. bound styrene, a specific gravity of        0.940 and a raw viscosity, ML-4 at 212° F of 46-58.               

A two-thirds portion of the rubber, zinc oxide and stearic acid weremixed on a warm mill (150°-160° F) for 5-8 minutes. Next,diphenylquanidine, N-cyclohexyl-2-benzothiozole-sulfenamide, and sulfurwere blended with the remaining one-third portion of rubber for 5-8minutes on a cool mill. The two mixtures were then combined with thefire retardant of Example 2 on a cool mill until well blended. Thecompounded stock was then cured 45 minutes at 292° F.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 6.

                  Table 6                                                         ______________________________________                                        Compound                                                                             Prepared          Styrene-       Burn                                         in                butadiene                                                                             Halogen                                                                              Rate                                         Example  Amounts  rubber  Content                                                                              (in/                                  Example                                                                              No.      (parts)  (parts) % wt.  min.)                                 ______________________________________                                        166    --       --       110.25  --     1.97                                  167    2         5       "       2.4    1.76                                  168    2        10       "       4.7    1.35                                  169    2        15       "       6.7    1.39                                  170    2        20       "       8.6    1.43                                  171    2        25       "       10.3   1.53                                  172    2        35       "       13.5   1.46                                  ______________________________________                                    

The results in Table 6 show that the fire retardant system of thepresent invention can reduce the burn rate of highly combustiblestyrene-butadiene rubber by about 25%. (Compare Example 166 withExamples 168 and 169.)

EXAMPLES 173-188

A series of samples were prepared by blending chlorendic anhydride, oneof the fire retardants of Examples, 1, 2, 31 or 45, and a 70/30styrene-acrylonitrile resin.

The samples were blended on a rubber mill at 310° F for 7 minutes andmolded at 310° F for 5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 7.

                  Table 7                                                         ______________________________________                                        Compound          Styrene-                                                           Prepared           acrylo-       Burn                                         in                 nitrile                                                                              Halogen                                                                              Rate                                         Example   Amounts  resin  Content                                                                              (in/                                  Example                                                                              No.       (parts)  (parts)                                                                              % wt.  min.)                                 ______________________________________                                        173    --        --       100    --     1.12                                                                          (avg.                                                                         of two)                               174    1         10       "      5.1    0.98                                  175    1         20       "      9.3    0.71                                  176    1         30       "      12.9   0.82                                  177    2         15.4     "      7.5    0.76                                  178    2         15.4     "      7.5    0.62                                  179    2         25       "      11.2   0.62                                  180    2         25       "      11.2   0.76                                  181    31        10       "      6.7    0.53                                  182    31        20       "      12.4   SE                                    183    31        30       "      17.1   SE                                    184    45        10       "      4.9    0.89                                  185    45        20       "      9.0    0.80                                  186    45        30       "      12.5   0.63                                  187    Chlorendic                                                                              15.4     "      7.7    0.77                                         anhydride                                                              188    Chlorendic                                                                              25       "      11.5   0.69                                         anhydride                                                              ______________________________________                                    

The results of Table 7 show that the fire retardant system of thepresent invention is at least as effective a fire retardant instyrene-acrylonitrile resin as is the prior art's chlorendic anhydride.Note the compound of Example 31 is markedly superior to chlorendicanhydride. (Compare Examples 181 and 182 with Examples 187 and 188.)

EXAMPLES 189-214

A series of samples were prepared by blending chlorendic anhydride orone of the fire retardants of Examples 1, 2 and 3 with polypropylene ofvarying molecular weights. The polypropylene had the followingcharacteristics:

    ______________________________________                                                                 Melt flow rate*                                      Type    Molecular Weight (dg/min)                                             ______________________________________                                        A       220,000          15.0                                                 B       325,000          4.0                                                  C       380,000          2.0                                                  D       470,000          0.8                                                  E       550,000          0.4                                                  ______________________________________                                         *Determind by ASTM D-1238-65T.                                           

The samples were milled at 345° F for 4 minutes and molded at 350° F for5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 8.

                  TABLE 8                                                         ______________________________________                                        Compound                                                                      Prepared                                                                      in                   Polypropy-                                                                              Halogen                                                                              Burn                                    Example     Amounts  lene      Content,                                                                             Rate                                    Ex.   No.       (parts)  Type Parts                                                                              % wt.  (in/min.)                           ______________________________________                                        189   --        --       C    100  --     0.70                                190   1           11.6   "    "    5.8    0.67                                191   1           15.4   "    "    7.5    0.46                                192   1           15.4   "    "    7.5    SE                                  193   1           25.0   "    "    11.1   SE                                  194   Chlorendic                                                                                15.4   "    "    7.7    0.40                                      anhydride                                                               195   --        --       "    "    --     1.03                                196   2         10       "    "    5.1    0.87                                197   2         15       "    "    7.3    0.66                                198   2         20       "    "    9.3    0.79                                199   2         25       "    "    11.2   SE                                  200   3         10       "    "    5.1    0.70                                201   3         15       "    "    7.3    0.66                                202   3         20       "    "     0.93  0.67                                203   --        --       A    100  --     1.26                                204   2         15       "    "    7.3    0.61                                205   2         20       "    "    9.3    0.84                                206   --        --       B    100  --     1.12                                207   2         15       "    "    7.3    0.58                                208   2         20       "    "    9.3    0.59                                209   --        --       D    100  --     1.38                                210   2         15       "    "    7.3    0.59                                211   2         20       "    "    9.3    0.58                                212   --        --       E    100  --     1.28                                213   2         15       "    "    7.3    0.71                                214   2         20       "    "    9.3    0.54                                ______________________________________                                    

As shown in Table 8, the fire retardant system of the present inventionsubstantially reduces the flammability of polypropylene.

EXAMPLES 215-230

A series of samples were prepared by blending the fire retardant ofExample 2 or chlorendic anhydride with Marlex 6050, a (Phillips) highmolecular weight, high density, linear homopolymer of ethylene.

The samples prepared from polyethylene were milled at 325° F for 5minutes, and molded at 340° F for 5 minutes.

The samples thus prepared were subjected to the oxygen index test. Theresults of these tests are set out in Table 9.

                                      TABLE 9                                     __________________________________________________________________________    Compound                                                                           Prepared                                                                      in                     Halogen                                                                            Oxygen                                            Example                                                                             Amounts          Content                                                                            Index                                        Example                                                                            No.   (parts)                                                                            Polymer (parts)                                                                           % wt.                                                                              %                                            __________________________________________________________________________    215  --    --   Marlex                                                                            6050                                                                              100 --   17.7                                         216  1     10   "       "   5.1  22.2                                         217  "     20   "       "   9.3  20.7                                         218  "     30   "       "   12.9 21.7                                         219  2      5   "       "   2.7  20.5                                         220  "     10   "       "   5.1  22.1                                         221  "     15   "       "   7.3  24.0                                         222  "     20   "       "   9.3  23.1                                         223  "     25   "       "   11.2 23.1                                         224  3     15   "       "   7.3  21.4                                         225  "     25   "       "   11.3 20.5                                         226  Chlorendic                                                                    anhydride                                                                            5   "       "   2.7  19.1                                         227  "     10   "       "   5.2  19.6                                         228  "     15   "       "   7.5  19.4                                         229  "     20   "       "   9.6  20.9                                         230  "     25   "       "   11.5 21.1                                         __________________________________________________________________________

EXAMPLES 231-241

A series of samples were prepared by blending the fire retardant ofExample 2 or 3 with ethylene-vinylacetate copolymer, EVA (DQD-1868). Theethylene-vinylacetate copolymer had the following characteristics:

    ______________________________________                                                      Shore                                                                         A         Specific Softening                                    Type          Hardness  Gravity  Point                                        ______________________________________                                        EVA (DQD-1868)                                                                              88        .943     64° C                                 (18% vinyl acetate)                                                           ______________________________________                                    

The samples were milled at 170° F for 5 minutes and molded at 212° F for5 minutes.

The samples thus prepared were subjected to the oxygen index test. Theresults of these tests are set out in Table 10.

                                      TABLE 10                                    __________________________________________________________________________    Compound                                                                           Prepared                                                                      in                      Halogen                                                                            Oxygen                                           Example                                                                             Amounts           Content                                                                            Index                                       Example                                                                            No.   (parts)                                                                            Polymer (parts)                                                                            % wt.                                                                              %                                           __________________________________________________________________________    231  --    --   EVA (DQD-1868)                                                                         100 --   18.8                                        232  2      5   "        "   2.7  19.4                                        233  "     10   "        "   5.1  22.7                                        234  "     15   "        "   7.3  28.4                                                                          avg. of 2                                   235  "     20   "        "   9.3  27.2                                        236  "     25   "        "   11.2 29.8                                        237  "     35   "        "   14.5 27.4                                                                          avg. of 2                                   238  3     15   "        "   7.3  20.5                                        239  "     25   "        "   11.3 20.6                                        240  Chlorendic                                                                            15.4                                                                             "        "   7.7  20.8                                             anhydride                                                                241  "     25   "        "   11.5 21.2                                        __________________________________________________________________________

EXAMPLES 242-245

A series of samples were prepared by blending the fire retardant ofExample 2 with Elvanol 50-42, a (DuPont) high molecular weight, coldwater soluble polyvinyl alcohol resin, having a 4% aqueous solutionviscosity of 35-45 at 20° C as determined by the Hoeppler falling ballmethod.

The polyvinyl alcohol was ground to 60 mesh and dry mixed with the fireretardant of Example 2 ground to 200 mesh. The dry mixture wascompression molded at 400° F for 5 minutes.

The samples thus prepared were subjected to oxygen index tests. Theresults of these tests are set out in Table 11.

                  TABLE 11                                                        ______________________________________                                        Compound                                                                            Prepared                                                                      in                          Halogen                                                                              Oxygen                                     Example  Amounts  Polyvinyl Content                                                                              Index                                Ex.   No.      (parts)  alcohol (parts)                                                                         % wt.  %                                    ______________________________________                                        242   --       --       100       --     22.48                                243   2         5       "         2.7    23.29                                244   2        10       "         5.1    25.46                                245   2        15       "         7.3    28.73                                ______________________________________                                    

EXAMPLES 246-286

A series of samples were prepared by blending either chlorendicanhydride or chloran or one of the fire retardants of Examples 1, 2, 3,25, 31 and 45, with four different types of polystyrene. Thesepolystyrenes were:

    __________________________________________________________________________                   Izod                                                                          impact                                                                  Melt  res.      Hardness                                                      Viscosity                                                                           (ft.lb/in Rockwell                                                                           Specific                                                                           Softening                                  Type     (poises)                                                                            notch at 73° F)                                                                  M    Gravity                                                                            Point                                      __________________________________________________________________________    A high heat,                                                                           2,700 0.20      71   1.04 220° F                                general                                                                       purpose                                                                     B high heat,                                                                           3,200 0.25      76   1.04 224° F                                general                                                                       purpose                                                                     C impact 2,850 0.90      38   1.05 190° F                                polystyrene                                                                 D high heat,                                                                           1,800 0.20      71   1.04 212° F                                general                                                                       purpose                                                                     __________________________________________________________________________

Samples were also prepared by blending polystyrene, the fire retardantof Example 2 and antimony oxide (Sb₂ O₃) in varying amounts.

The samples were milled at 330° F for 5 minutes and molded at 320° F for5 minutes.

The samples thus prepared were subjected to burn rate and oxygen indextests. The results of these tests are set out in Table 12.

                                      TABLE 12                                    __________________________________________________________________________    Compound                                                                      Prepared                     Burn                                             in                      Halogen                                                                            Rate Oxygen                                      Example    Amounts                                                                            Polystyrene                                                                           Content                                                                            (in/ Index                                       Example                                                                            No.   (parts)                                                                            type                                                                             (parts)                                                                            % wt.                                                                              min.)                                                                              %                                           __________________________________________________________________________    246  --    --   A  100  0    0.88 17.6                                        247  2       15.4                                                                             "  "    7.5  SE   --                                          248  2       25.0                                                                             "  "    11.2 SE   --                                          249  Chlorendic                                                                            15.4                                                                             "  "    7.7  0.91 20.4                                             anhydride                                                                250  Chlorendic                                                                            25.0                                                                             "  "    11.5 0.60 18.9                                             anhydride                                                                251  --    --   C  "    0    --   17.8                                        252  2       17.7                                                                             "  "    8.4  --   25.9                                         253*                                                                              2       11.6                                                                             "  "    5.6  --   25.9                                         254*                                                                              2       19.0                                                                             "  "    8.4  --   26.7                                        255  Chloran                                                                               20.5                                                                             "  "    8.5  --   19.6                                         256*                                                                              Chloran                                                                               21.5                                                                             "  "    8.9  --   25.8                                        257  --    --   B  "    0    1.34 --                                          258  1     10   "  "    5.1  1.11 --                                          259  1     13   "  "    7.3  0.90 --                                          260  1     20   "  "    9.3  0.64 --                                          261  2      5   "  "    2.7  1.12 --                                          262  2     10   "  "    5.1  1.07 --                                          263  2     20   "  "    9.3  0.58 --                                          264  2     25   "  "    11.2 Non- --                                                                       burning                                          265  3      5   "  "    2.7  1.22 --                                          266  3     10   "  "    5.1  1.18 --                                          267  3     15   B  "    7.3  SE   --                                          268  25    15   B  100  7.8  SE   --                                          269  31    10   "  "    6.7  Non- --                                                                       burning                                          270  31    15   "  "    9.5  Non- --                                                                       burning                                          271  45    10   "  "    4.9  0.97 --                                          272  45    15   "  "    7.0  0.71 --                                          273  45    20   "  "    9.0  0.82 --                                          274  Chlorendic                                                                          15   "  "    7.5  1.26 --                                               anhydride                                                                275  Chlorendic                                                                          25   "  "    11.5 0.70 --                                               anhydride                                                                276  --    --   D  "    0    1.11 --                                          277  2      5   "  "    2.7  0.87 --                                          278  2     10   "  "    5.1  0.73 --                                          279  2     15   "  "    7.3  0.84 --                                          280  2     15   "  "    7.3  0.71 --                                          281  2     20   "  "    9.3  0.68 --                                          282  2     25   "  "    11.3 0.57 --                                          283  3     15   "  "    7.3  0.65 --                                          284  3     25   "  "    11.3 SE   --                                          285  Chlorendic                                                                          15   "  "    7.5  1.20 --                                               anhydride                                                                286  Chlorendic                                                                          25   "  "    11.5 1.13 --                                               anhydride                                                                __________________________________________________________________________     *In Examples 253, 254 and 256, the compounds also contained 4.7, 7.6 and      5.1 parts, respectively, of Eb.sub.2 O.sub.3.                            

From Table 12, it is apparent that the addition of relatively smallamounts of antimony oxide substantially enhances the effect of the fireretardant system of the present invention. Thus, identical oxygen indexvalues are obtained in Example 252 and Example 253, even though thepolymer of Example 253, which contained Sb₂ O₃, contained 1/3 less ofthe fire retardant of Example 2 than did the polymer of Example 252.

EXAMPLES 287-291

A series of samples were prepared by blending either the fire retardantof Example 2 or chlorendic anhydride with poly-alpha-methyl-styrene. Thepoly-alpha-methyl-styrene had a number average molecular weight of100,000.

The samples were milled at 330° F for 7 minutes and molded at 330° F for5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 13.

                  TABLE 13                                                        ______________________________________                                        Compound                                                                            Prepared                                                                      in                 Poly-alpha-                                                                           Halogen                                                                              Burn                                        Example   Amounts  methyl-sty-                                                                           Content,                                                                             Rate                                  Ex.   No.       (parts)  rene (parts)                                                                          % wt.  (in/min.)                             ______________________________________                                        287   --        --       100     0      2.49                                  288   2         15       100     7.3    2.09                                  289   2         25       100     11.2   1.89                                  290   Chlorendic                                                                              15       100     7.5    2.11                                        anhydride                                                               291   Chlorendic                                                                              25       100     11.5   1.88                                        anhydride                                                               ______________________________________                                    

The results in Table 13 show that in poly-alpha-methyl-styrene, thesystem of the present invention is at least as effective as chlorendicanhydride.

EXAMPLES 292-294

A series of samples were prepared by blending the fire retardant ofExample 2 with a polysulfone. The polysulfone was prepared frombisphenol-A and dichlorodiphenyl sulfone and had a heat distortiontemperature of 181° C at 66 psi.

The samples were milled at 450° F for 10 minutes and molded at 450° Ffor 5 minutes.

The samples thus prepared were subject to burn rate and oxygen indextests as hereinabove described. The results of these tests are set outin Table 14.

                  TABLE 4                                                         ______________________________________                                        Compound                                                                           Prepared                       Burn                                           in                Poly- Halogen                                                                              Rate   Oxygen                                  Example  Amounts  sulfone                                                                             Content                                                                              (in/   Index                              Ex.  No.      (parts)  (parts)                                                                             % wt.  min.)  %                                  ______________________________________                                        292  --       --       100   0      Non    32.4                                                                   Burning                                   293  2         7.5     100   3.9     "     45.2                               294  2        15.4     100   7.5     "     32.0                               ______________________________________                                    

The results in Table 14 show that although the unprotected polysulfoneis non-burning by the burn rate test, there is a marked decrease inflammability as measured by the oxygen index test of a polysulfonecontaining the fire retardant system of the present invention. Note,however, that the fire retardancy does not continue to increase withincreasing halogen content. Thus, the flammability of the polysulfonecontaining the fire retardant system is lowest at a level of 7.5 partsof the system per 100 parts of polysulfone. As the amount of fireretardant system in the polysulfone is increased, however, theflammability of the composition increases.

EXAMPLES 295-297

A series of samples were prepared by blending the fire retardant ofExample 2 with a polycarbonate. The polycarbonate was a thermoplasticcarbonate linked polymer obtained from the reaction of bisphenol-A andphosgene and having a heat distortion temperature of 143° C at 66 psi.

The samples were milled at 500°-550° F for 10 minutes and molded at500°-550° F for 5 minutes.

The samples thus prepared were subjected to burn rate and oxygen indextests as described hereinabove. The results of these tests are set outin Table 15.

                  TABLE 15                                                        ______________________________________                                        Compound                                                                           Prepared                        Burn                                          in                Polycar-                                                                             Halogen                                                                              Rate  Oxygen                                  Example  Amounts  bonate Content,                                                                             (in/  Index                              Ex.  No.      (parts)  (parts)                                                                              % wt.  min.) %                                  ______________________________________                                        295  --       --       100    0      SE    24.8                               296  2         7.5     100    3.9    SE    29.9                               297  2        15.4     100    7.5    SE    26.7                               ______________________________________                                    

As shown in Table 15 the flammability of the polycarbonate polymer isreduced when the fire retardant system of the present invention isblended therewith.

EXAMPLES 298-302

A series of samples were prepared by blending the fire retardant ofExample 2 or chlorendic anhydride with a cellulose ester. The celluloseester was prepared from cellulose acetate butyrate. (TeniteButyrate-Eastman).

The samples were milled at 350° F for 4 minutes and molded at 350° F for5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 16.

                  TABLE 16                                                        ______________________________________                                        Compound                                                                           Prepared                                                                      in                 Cellulose                                                                             Halogen                                            Example   Amounts  Ester   Content,                                                                             Burn Rate                              Ex.  No.       (parts)  (parts) % wt.  (in/min.)                              ______________________________________                                        298  --        --       100     0      0.89                                   299  2         15.4     100     7.5    0.73                                   300  2         25       100     11.2   0.69                                   301  Chlorendic                                                                              15.4     100     7.7    0.90                                        Anhydride                                                                302  Chlorendic                                                                              25       100     11.5   0.86                                        Anhydride                                                                ______________________________________                                    

The results in Table 16 show the superiority of the fire retardantsystem of the present invention in a cellulose ester polymer as comparedwith the effect of chlorendic anhydride in such polymer.

EXAMPLES 303-305

A series of samples were prepared by blending the fire retardants ofExamples 1 and 2 with polyvinylchloride plasticized withdioctylphthalate.

The samples were milled at 315° F for 5 minutes and molded at 315° F for5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 17.

                                      TABLE 17                                    __________________________________________________________________________                   Plasticized                                                    Compound       polyvinyl-                                                     Prepared       chloride                                                            in             dioctyl                                                                             Halogen                                                  Example                                                                            Amounts                                                                            PVC  phthalate                                                                           Content                                                                            Burn Rate                                      Example                                                                            No.  (parts)                                                                            (parts)                                                                            (parts)                                                                             % wt.                                                                              (in/min.)                                      __________________________________________________________________________    303  --   --   100  100   28.4 burned                                         304  1    8    "    "     29.4 SE                                             305  2    5    "    "     29.0 1.25                                           __________________________________________________________________________

The results in Table 17 show the marked decrease in the flammability ofplasticized polyvinylchloride when the fire retardant system of thepresent system is blended therewith. This effect is particularlysignificant in view of the increased use of plasticizedpolyvinylchloride polymers for high temperature uses such as crash padsand the like.

EXAMPLES 306-316

A series of samples were prepared by blending the fire retardant ofExamples 2 and 45 with two types of epoxy resin. One epoxy resin was thecondensation product of epichlorohydrin and bisphenol A (Epon 815,Shell), and the other was the epoxide of bis-cyclopentenyl ether (ERLA4305).

The samples were prepared by mixing the epoxy resin with the fireretardant compound and meta-phenylene diamine at 176° F, curing the Epon815 resin for 2 hours at 212° F and then for 2 hours at 300° F, andcuring the ERLA 4305 resin for 2 hours at 212° F and then for 16 hoursat 310° F.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 18.

                                      TABLE 18                                    __________________________________________________________________________    Compound                                                                      Prepared               Meta-                                                  in                     pheny-                                                                             Halogen                                           Example   Amounts                                                                            Epoxy Resin                                                                           lene Content                                                                            Burn Rate                                    Example                                                                            No.  (parts)                                                                            Type                                                                              Parts                                                                             diamine                                                                            % wt.                                                                              (in/min.)                                    __________________________________________________________________________    306  --   --   Epon                                                                              87.5                                                                              12.5 0    0.76                                                        815               avg. of 2                                    307  2    5    "   "   "    2.7  SE                                           308  2    10   "   "   "    5.1  SE                                           309  2    20   "   "   "    9.3  0.97                                         310  45   5    "   "   12.7 2.7  SE                                           311  45   10   "   "   "    5.1  SE                                           312            ERLA                                                                              86  14   0    0.78                                                        4305              avg. of 2                                    313  2    5    "   "   "    2.7  0.86                                         314  2    10   "   "   "    5.1  0.83                                         315  2    15   "   "   "    7.3  SE                                           316  2    20   "   "   "    9.3  Non-                                                                          Burning                                      __________________________________________________________________________

The results in Table 18 show the fire retardant effect of the system ofthe present invention on two different types of epoxy resin. Note thatin the Epon 815, the maximum effect is obtained at a level of 5-10 partsof fire retardant compound to 87.5 parts of resin.

EXAMPLES 317-318

A series of samples were prepared by blending the fire retardant ofExample 2 with polyethylene terephthalate having an intrinsic viscosityof 0.93 in 60/40 phenol-tetrachlorethane.

The samples were milled at 500° F for 10 minutes and molded at 500° Ffor 5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 19.

                  TABLE 19                                                        ______________________________________                                        Compound                                                                           Prepared                                                                      in                Polyethylene                                                                           Halogen                                            Example  Amounts  terephthalate                                                                          Content                                                                              Burn Rate                              Ex.  No.      (parts)  (parts)  % wt.  (in/min.)                              ______________________________________                                        317  --       --       100      0      0.56                                   318  2        15.4     100      7.5    SE                                     ______________________________________                                    

The results in Table 19 demonstrate the marked decrease in flammabilityof polyethyleneterephthalate when blended with the fire retardant systemof the present invention.

EXAMPLES 319-355

A series of samples were prepared by blending chlorendic anhydride orone of the fire retardants of Examples 1,2,3,25,31,45, and 47 with aliquid cast polyurethane based on castor oil (Type C) or on ThanolF-3000, i.e., a polypropylene ether glycol (Type D) or with athermoplastic polyurethanes based on polyether (Type A; Roylar A-855;Uniroyal) and based on polyester (Type B; Roylar S-4; Uniroyal). RoylarA-855 is a high hardness urethane thermoplastic which is based onpolytetramethylene ether glycol and has a hardness of 91A and a specificgravity of 1.12. Roylar S-4 has a hardness of 40D and a specific gravityof 1.23.

Type C liquid cast polyurethanes were prepared by dissolving the fireretardant and 0.1 part of triethylene diamine (catalyst) in the CO(castor oil-Baker Castor Oil Co., D.B. grade). The solution was cooledto 40° C and TD1 (80/20 ratio of 2,4- and 2,6- toluene diisocyanateisomers) was mixed in by rapid stirring. The mixture was immediatelypoured into a 6×6×1/8 inch mold and cured for one hour at 140° C.

Type D liquid cast polyurethanes were prepared similarly except that thecastor oil was replaced by Thanol F-3000 (Jefferson Chem. Co.polypropylene glycol of 3000 molecular weight and 1000 hydroxylequivalent weight) and the Thanol solution was cooled at 80° C beforemixing in TD1.

The samples with Type A were milled at 335° F for 4 minutes and moldedat 350° F for 5 minutes. The samples with Type B were milled at 380° Ffor 4 minutes and molded at 350° F for 5 minutes.

The samples thus prepared were subjected to burn rate tests. The resultsof these tests are set out in Table 20.

                                      TABLE 20                                    __________________________________________________________________________    Compound                                                                      Prepared                                                                      in                        Halogen                                             Example    Amounts                                                                            Polyurethane                                                                            Content,                                                                           Burn Rate                                      Example                                                                            No.   (parts)                                                                            Type                                                                              (parts)                                                                             % wt.                                                                              (in/min.)                                      __________________________________________________________________________    319  --    --   A   100   0    1.12                                                                          Average                                                                       of two                                         320  2     5    "   "     2.7  SE                                             321  2     10   "   "     5.1  Non                                                                           Burning                                        322  2     15.4 "   "     7.5  Non                                                                           Burning                                        323  2     25   "   "     11.2 Non                                                                           Burning                                        324  3     10   "   "     5.1   "                                             325  3     15   "   "     7.3   "                                             326  31    15   "   "     9.5  1.38                                           327  31    25   "   "     14.8 1.52                                           328  45    5    "   "     2.6  0.87                                           329  45    10   "   "     4.9  Non                                                                           Burning                                        330  45    15   "   "     7.0  Non                                                                           Burning                                        331  47    15   "   "     6.4  1.36                                           332  47    25   "   "     9.9  1.44                                           333  Chlorendic                                                                          15.4 "   "     7.7  0.68                                                anhydride                                                                334  Chlorendic                                                                          25.0 "   "     11.5 0.80                                                anhydride                                                                335  --    --   C   CO 82.0    1.80                                                               TDI 21.8                                                  336  1     10   C   CO 82.0                                                                             4.9  1.21                                                               TDI 21.8                                                  337  1     15   C   CO 82.0                                                                             7.1  1.07                                                               TDI 21.8                                                  338  1     20   C   CO 82.0                                                                             9.0  0.87                                                               TDI 21.8                                                  339  2     5    "   CO 77.2                                                                             2.7  0.69                                                               TDI 23.0                                                  340  2     10   "   CO 75.3                                                                             5.1  0.74                                                               TDI 24.9                                                  341  2     15   "   CO 73.4                                                                             7.3  SE                                                                 TDI 26.8                                                  342  2     20   "   CO 71.5                                                                             9.3  SE                                                                 TDI 28.7                                                  343  2     25   "   CO 69.5                                                                             11.3 SE                                                                 TDI 30.6                                                  344  47    10   "   CO 82.0                                                                             4.3  1.20                                                               TDI 21.8                                                  345  47    15   "   CO 82.0                                                                             6.4  1.01                                                               TDI 21.8                                                  346             D   Thanol 92.0                                                                         0    1.71                                                               TDI 8.0                                                   347  2     10   "   Thanol 88.0                                                                         5.1  0.70                                                               TDI 12.2                                                  348  2     15   "   Thanol 85.5                                                                         7.3  SE                                                                 TDI 14.4                                                  349  --    --   B   100   0    0.94                                                                          avg. of 2                                      350  2     15.2 "   "     7.5  SE                                             351  2     25   "   "     11.2 SE                                             352  3     10   "   "     5.1  SE                                             353  3     15   "   "     7.3  SE                                             354  25    10   "   "     5.4  SE                                             355  25    15   "   "     7.8  SE                                             __________________________________________________________________________

As shown in Table 20, the effect of the fire retardant system of thepresent invention on a polyurethane based polyether, i.e., Type A., issubstantial, inasmuch as at relatively low levels of fire retardantcompound the polymer is rendered completely non-burning. Forpolyurethanes based on castor oil, (Type C), Thanol F3000, (Type D), andpolyurethanes based on polyesters, (Type B), when blended with the fireretardant system of the present invention, the polyurethane is renderedeither self-extinguishing or the flammability thereof is substantiallydecreased.

EXAMPLES 356-358

A series of samples were prepared by blending the fire retardant ofExample 2 with BKR-2620, (Union Carbide) a predominantly unmodified,heat reactive phenol-formaldehyde resin having a specific gravity of 25°C of 1.23-1.25, a softening point of 180°-210° F by the ball and ringmethod, and a Gardner Color (1933 scale) of 12 maximum on a 50% solidssolution in ethanol.

The phenol-formaldehyde resin was ground to 200 mesh and dry mixed withthe fire retardant of Example 2 to 200 mesh. The dry mixture wascompression molded at 350° F for 30 minutes.

The samples thus prepared were subjected to oxygen index tests. Theresults of these tests are set out in Table 21.

                  TABLE 21                                                        ______________________________________                                        Compound                                                                            Prepared                                                                      in                Phenol-   Halogen                                                                              Oxygen                                     Example  Amount   formaldehyde                                                                            Content                                                                              Index                                Ex.   No.      (parts)  resin (parts)                                                                           % wt.  %                                    ______________________________________                                        356   --       --       100       --     24.57                                357   2         5       "         2.7    26.67                                358   2        10       "         5.1    27.88                                ______________________________________                                    

Variations and modifications can, of course, be made without departingfrom the spirit and scope of the present invention.

What is claimed is:
 1. A compound having the formula: ##STR96## whereinR₁₉ and R₂₀ are both ##STR97## wherein R₂₉ is lower alkyl, R₂₁ and R₂₂are both hydrogen and X is halogen.
 2. A compound as claimed in claim 1,wherein R₂₉ is methyl and X is chlorine.
 3. A compound as claimed inclaim 1, wherein R₂₉ is ethyl and X is chlorine.
 4. A compound asclaimed in claim 1, wherein R₂₉ is nonyl and X is chlorine.
 5. Acompound as claimed in claim 1, wherein R₂₉ is tert-butyl and X ischlorine.
 6. A compound as claimed in claim 1, wherein R₂₉ is methyl andX is bromine.